CN106868589A - K3Sr3Li2Al4B6O20F compounds, nonlinear optical crystal and its preparation method and purposes - Google Patents

K3Sr3Li2Al4B6O20F compounds, nonlinear optical crystal and its preparation method and purposes Download PDF

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CN106868589A
CN106868589A CN201710043576.XA CN201710043576A CN106868589A CN 106868589 A CN106868589 A CN 106868589A CN 201710043576 A CN201710043576 A CN 201710043576A CN 106868589 A CN106868589 A CN 106868589A
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nonlinear optical
crystal
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罗军华
赵三根
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Fujian Institute of Research on the Structure of Matter of CAS
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
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    • C01B35/10—Compounds containing boron and oxygen
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/02—Production of homogeneous polycrystalline material with defined structure directly from the solid state
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B9/00—Single-crystal growth from melt solutions using molten solvents
    • C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
    • C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/3551—Crystals

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Abstract

The present invention relates to a kind of K3Sr3Li2Al4B6O20F compounds, K3Sr3Li2Al4B6O20F nonlinear optical crystals and its preparation method and purposes.The method have the advantages that：With the speed of growth is very fast, low cost and other advantages；The crystal for being obtained has the advantages that shorter UV absorption cut-off side, larger nonlinear optical effect, physical and chemical performance stabilization, good mechanical property, easy to process；The crystal can be used to make device for non-linear optical；The device for non-linear optical that nonlinear optical crystal of the present invention makes can be used in some military and civilian high-tech areas, such as blinding laser weapons, video disc recording, laser projection tv, optical oomputing and optical-fibre communications etc..

Description

K3Sr3Li2Al4B6O20F compounds, nonlinear optical crystal and its preparation method and purposes
Technical field
The present invention relates to a kind of K3Sr3Li2Al4B6O20F compounds, K3Sr3Li2Al4B6O20F nonlinear optical crystals, K3Sr3Li2Al4B6O20The preparation method and K of F crystal3Sr3Li2Al4B6O20F crystal is used to make the use of device for non-linear optical On the way.
Technical background
The nonlinear optical effect of crystal refers to such a effect：When a branch of laser with certain polarization direction presses one When determining direction by one block of nonlinear optical crystal, the frequency of the light beam will change.Crystalline substance with nonlinear optical effect Body is referred to as nonlinear optical crystal.Using the nonlinear optical effect of crystal, second harmonic generator and upper and lower frequency can be made The device for non-linear optical such as rate converter and optical parametric oscillator.The complete solid of frequency transformation is carried out using nonlinear optical crystal State laser is a developing direction of following laser, and it is critical only that and obtains outstanding nonlinear optical crystal.
At present, the nonlinear optical crystal for being applied to ultraviolet band mainly has β-BaB2O4(BBO)、LiB3O5(LBO)、 CsLiB6O10And K (CLBO)2Be2BO3F2(KBBF) etc., but all there is respective weak point in them.For example, the birefringence of LBO Rate is all smaller, it is impossible to realize the quadruple output of 1064nm wavelength lasers；The birefringence of BBO is bigger than normal, for 1064nm ripples There is photorefractive effect in the quadruple of laser long, limit its power output and beam quality when exporting；And CLBO easily deliquescence, It is difficult to commercial applications；KBBF causes it to be difficult to obtain c to the big crystalline substance of thickness then due to its serious layer growth habit Body.Therefore, it is still urgent and necessary to explore the new ultra-violet nonlinear optical crystal of excellent combination property.
The theoretical, (BO containing conjugatedπbond according to anionic group3)3-Group has relatively large microcosmic Clock Multiplier Factor, when These (BO3)3-Group orientation can produce big macroscopical Clock Multiplier Factor when consistent；Meanwhile, its plane configuration is conducive to producing Larger birefringence is realizing the phase matched of ultraviolet band；In addition, (BO3)3-Group has band gap wider, is conducive to ultraviolet The raising of the transmission and threshold for resisting laser damage of light.Therefore, (BO3)3-Group is considered as that design synthesis is ultraviolet and deep ultraviolet is non- One of optimal group of linear optical crystal.The currently the only crystal KBBF for being capable of direct frequency doubling output deep ultraviolet laser, its base This structural motif is (BO3)3-Group.In KBBF crystal structures, by (BO3)3-With (BeO3F)5-Between the plane layer constructed By K+–F-Ionic bond is connected, and attachment force is weaker, and this causes KBBF crystal to show serious layer growth habit.
Therefore, a kind of new ultra-violet nonlinear optical material of inventor's design synthesis：In the material crystal structure, (BO3)3-Group is parallel to each other and orientation is basically identical so that it has larger frequency-doubled effect and can be in ultra-violet (UV) band reality Existing phase matched；On the other hand, it is bonded by Sr-O between layers and is connect, more closely, gained new material will not has for interlayer connection There is layer growth habit.Based on this, the present inventor completes the present invention on the basis of a large amount of exploration.Crystal structure analysis and Powder frequency doubling test etc. all shows that this design is practicable.
The content of the invention
It is K it is an object of the invention to provide a kind of chemical formula3Sr3Li2Al4B6O20The compound of F.
It is another object of the present invention to provide a kind of K3Sr3Li2Al4B6O20F nonlinear optical crystals.
It is yet a further object of the present invention to provide K3Sr3Li2Al4B6O20The preparation method of F crystal.
A further object of the present invention is to provide K3Sr3Li2Al4B6O20The purposes of F nonlinear optical crystals.
Technical scheme is as follows.
(1) a kind of K3Sr3Li2Al4B6O20The compound of F, described K3Sr3Li2Al4B6O20The chemical formula of F compounds is K3Sr3Li2Al4B6O20F。
(2) a kind of K3Sr3Li2Al4B6O20The preparation method of F compounds, described using solid reaction process preparation K3Sr3Li2Al4B6O20F compounds, described solid reaction process comprises the following steps：
K compounds, compound containing Sr, compound containing Li, compound containing Al, boride alloy and compound containing F will be contained to change After metering is learned than uniform mixing, 450-650 DEG C is warmed up to 10-200 DEG C/h of speed, then heat preservation sintering 12 hours with On, be down to after room temperature that to take out grinding uniform, then with 10-200 DEG C/h of speed be warmed up to 600-800 DEG C of sintering 24 hours with On, grinding more than 1 time is taken out in midway, obtains final product the K of pure phase3Sr3Li2Al4B6O20F compounds.
Further, the compound containing K is K2CO3、KNO3Or KHCO3；The compound containing Sr is SrCO3、Sr(OH)2 Or Sr (NO3)2；The compound containing Li is Li2CO3Or LiOHH2O；The compound containing Al is Al2O3；The chemical combination containing B Thing is H3BO3；The compound containing F is LiF, KBF4, KF or SrF2。
K can be typically obtained the following is several3Sr3Li2Al4B6O20The reaction of F compounds：
(a)1.5K2CO3+3SrCO3+0.5Li2CO3+2Al2O3+6H3BO3+LiF
=K3Sr3Li2Al4B6O20F+2CO2↑+9H2O↑+3O2↑
(b)11KNO3+12Sr(OH)2+8LiOH·H2O+8Al2O3+23H3BO3+KBF4
=4K3Sr3Li2Al4B6O20F+11NO2↑+58.5H2O↑+2.75O2↑
(c)2KHCO3+3Sr(NO3)2+Li2CO3+2Al2O3+6H3BO3+KF
=K3Sr3Li2Al4B6O20F+3CO2↑+10H2O↑+6NO2↑+1.5O2↑
(d)3K2CO3+5SrCO3+2Li2CO3+4Al2O3+12H3BO3+SrF2
=2K3Sr3Li2Al4B6O20F+10CO2↑+18H2O↑。
Further, described K3Sr3Li2Al4B6O20F nonlinear optical crystals are free of symmetrical centre, belong to trigonal system R32 Space group, cell parameter is α=90.00, β=90.00, γ=120.00, V=1532.59 (12)3, Z=3.
Further, using the K that flux growth metrhod growth is described3Sr3Li2Al4B6O20F nonlinear optical crystals, including it is as follows Step：
It is 7.5~15.5 by mol ratio:1 flux and K3Sr3Li2Al4B6O20F raw materials of compound is put into crucible, is stirred Mix uniform, will then fill flux and K3Sr3Li2Al4B6O20The crucible of the mixture that F raw materials of compound is mixed is placed in In crystal growing furnace, be slowly warmed up to more than 750 DEG C, be incubated more than 12 hours, then slow cooling, on high-temperature fusant surface or Crystal is grown in melt.
Further, described flux is Li2O、SrF2And H3BO3It is 3~6 according to mol ratio:0.5~1.5:4~8 Mix.
Further, described K3Sr3Li2Al4B6O20F nonlinear optical crystals can be used as device for non-linear optical.
Further, described device for non-linear optical is by described K3Sr3Li2Al4B6O20F nonlinear optical crystal systems It is standby to form.
K of the invention3Sr3Li2Al4B6O20The purposes of F nonlinear optical crystals, including make as device for non-linear optical With.
Preferably, prepared device for non-linear optical is included and at least a branch of incidence electromagnetic radiation to pass through at least one piece K3Sr3Li2Al4B6O20After F nonlinear optical crystals, at least a branch of frequency is produced to be different from the output radiation of incidence electromagnetic radiation Device.
The K3Sr3Li2Al4B6O20There is F nonlinear optical crystals physical and chemical performance to stablize, hardness is moderate, mechanical performance Good, not easily broken, easy to process the advantages of；So the invention furthermore provides K3Sr3Li2Al4B6O20F non-linear optical crystals The purposes of body, it is the K3Sr3Li2Al4B6O20F7Nonlinear optical crystal is used to prepare device for non-linear optical.
K of the invention3Sr3Li2Al4B6O20F compounds, nonlinear optical crystal of the compound and preparation method thereof and Purposes has the advantages that：
(1) K for being obtained3Sr3Li2Al4B6O20F nonlinear optical crystals have shorter UV absorption cut-off side, larger Nonlinear optical effect, physical and chemical performance stabilization, good mechanical property, it is easy to process the advantages of；
(2) K3Sr3Li2Al4B6O20F nonlinear optical crystals can be used to make device for non-linear optical；
(3) device for non-linear optical that nonlinear optical crystal of the present invention makes can be used for some military and civilian high-tech In field, such as blinding laser weapons, video disc recording, laser projection tv, optical oomputing and optical-fibre communications etc..
Brief description of the drawings
Fig. 1 is to use K3Sr3Li2Al4B6O20The fundamental diagram of a kind of typical device for non-linear optical that F crystal is made, Wherein 1 is laser, and 2 is incoming laser beam, and 3 is the K through crystal post processing and optical manufacturing3Sr3Li2Al4B6O20F crystal, 4 It is produced laser beam, 5 is optical filter.
Fig. 2 is K of the invention3Sr3Li2Al4B6O20F polycrystal powders X ray diffracting spectrum be based on K3Sr3Li2Al4B6O20F The X ray diffracting spectrum of crystal structure simulation.
Fig. 3 is K of the invention3Sr3Li2Al4B6O20F crystal structure figures.
Specific embodiment
The present invention is further described with reference to embodiment and accompanying drawing.Those skilled in the art know that following embodiments are not It is limiting the scope of the invention, any improvement made on the basis of the present invention and change are all in protection model of the invention Within enclosing.
Embodiment 1-4 is on powdered K3Sr3Li2Al4B6O20The preparation of F compounds.
Embodiment 1
Using solid reaction process, reaction equation is as follows：
(a)1.5K2CO3+3SrCO3+0.5Li2CO3+2Al2O3+6H3BO3+LiF
=K3Sr3Li2Al4B6O20F+2CO2↑+9H2O↑+3O2↑
Above-mentioned three kinds of reagent inventorys：K2CO3 20.73g(0.15mol),SrCO3 44.28g(0.30mol),Li2CO3 3.69g(0.05mol),Al2O3 20.39g(0.20mol),LiF 2.59g(0.10mol),and H3BO3 37.08g (0.6mol)。
Concrete operation step is：Reagent is weighed respectively by above-mentioned dosage, is placed them into mortar, mix and grind It is even, it is then charged into corundum ceramic crucible, it is compacted into, it is put into Muffle furnace, 450 DEG C are warmed up to 10 DEG C/h of speed, Then heat preservation sintering more than 12 hours, take out grinding uniformly, then be warmed up to 600 DEG C with 10 DEG C/h of speed after being down to room temperature Grinding more than 1 time is taken out in sintering more than 24 hours, midway, obtains final product the K of pure phase3Sr3Li2Al4B6O20F compounds.
As shown in Fig. 2 the x-ray diffractogram of powder spectrum obtained by experiment and the collection of illustrative plates one according to obtained by the fitting of its mono-crystalline structures Cause.
Embodiment 2
Prepare powdered K3Sr3Li2Al4B6O20F compounds
Using solid reaction process, reaction equation is as follows：
(b)11KNO3+12Sr(OH)2+8LiOH·H2O+8Al2O3+23H3BO3+KBF4
=4K3Sr3Li2Al4B6O20F+11NO2↑+58.5H2O↑+2.75O2↑
Above-mentioned three kinds of reagent inventorys：
0.11mol KNO3、0.12mol Sr(OH)2、0.08mol LiOH·H2O、0.08mol Al2O3、0.23mol H3BO3、0.01mol KBF4。
Concrete operation step is：Reagent is weighed respectively by above-mentioned dosage, is placed them into mortar, mix and grind It is even, it is then charged into corundum ceramic crucible, it is compacted into, it is put into Muffle furnace, it is warmed up to 650 with 200 DEG C/h of speed DEG C, then heat preservation sintering more than 12 hours, take out grinding uniformly, then be warmed up to 200 DEG C/h of speed after being down to room temperature 800 DEG C sinter more than 24 hours, and grinding more than 1 time is taken out in midway, obtains final product the K of pure phase3Sr3Li2Al4B6O20F compounds.
Embodiment 3
Prepare powdered K3Sr3Li2Al4B6O20F compounds
Using solid reaction process, reaction equation is as follows：
(c)2KHCO3+3Sr(NO3)2+Li2CO3+2Al2O3+6H3BO3+KF
=K3Sr3Li2Al4B6O20F+3CO2↑+10H2O↑+6NO2↑+1.5O2↑。
Above-mentioned three kinds of reagent inventorys：
0.2mol KHCO3、0.3mol Sr(NO3)2、0.1mol Li2CO3、0.2mol Al2O3、0.6mol H3BO3、 0.1mol KF。
Concrete operation step is：Reagent is weighed respectively by above-mentioned dosage, is placed them into mortar, mix and grind It is even, it is then charged into corundum ceramic crucible, it is compacted into, it is put into Muffle furnace, it is warmed up to 550 with 100 DEG C/h of speed DEG C, then heat preservation sintering more than 12 hours, take out grinding uniformly, then be warmed up to 100 DEG C/h of speed after being down to room temperature 700 DEG C sinter more than 24 hours, and grinding more than 1 time is taken out in midway, obtains final product the K of pure phase3Sr3Li2Al4B6O20F compounds.
Embodiment 4
Prepare powdered K3Sr3Li2Al4B6O20F compounds
Using solid reaction process, reaction equation is as follows：
(d)3K2CO3+5SrCO3+2Li2CO3+4Al2O3+12H3BO3+SrF2
=2K3Sr3Li2Al4B6O20F+10CO2↑+18H2O↑。
Above-mentioned three kinds of reagent inventorys：0.3mol K2CO3、0.5mol SrCO3、0.2mol Li2CO3、0.4mol Al2O3、1.2mol H3BO3With 0.1mol SrF2
Concrete operation step is：Reagent is weighed respectively by above-mentioned dosage, is placed them into mortar, mix and grind It is even, it is then charged into corundum ceramic crucible, it is compacted into, it is put into Muffle furnace, 500 DEG C are warmed up to 50 DEG C/h of speed, Then heat preservation sintering more than 12 hours, take out grinding uniformly, then be warmed up to 750 DEG C with 50 DEG C/h of speed after being down to room temperature Grinding more than 1 time is taken out in sintering more than 24 hours, midway, obtains final product the K of pure phase3Sr3Li2Al4B6O20F compounds.
Embodiment 5-8 is to prepare K3Sr3Li2Al4B6O20F crystal
Embodiment 5
Using the described K of flux growth metrhod growth3Sr3Li2Al4B6O20F nonlinear optical crystals, comprise the following steps：
It is 7.5 by mol ratio:1 flux and K3Sr3Li2Al4B6O20F raw materials of compound is put into crucible, and stirring is equal It is even, will then fill flux and K3Sr3Li2Al4B6O20The crucible of the mixture that F raw materials of compound is mixed is placed in crystal In growth furnace, more than 750 DEG C are slowly warmed up to, more than 12 hours are incubated, then slow cooling, in high-temperature fusant surface or melt Middle growth crystal.
Described flux is Li2O、SrF2And H3BO3It is 3 according to mol ratio:0.5:4 mix.
Embodiment 6
Using the described K of flux growth metrhod growth3Sr3Li2Al4B6O20F nonlinear optical crystals, comprise the following steps：
It is 15.5 by mol ratio:1 flux and K3Sr3Li2Al4B6O20F raw materials of compound is put into crucible, and stirring is equal It is even, will then fill flux and K3Sr3Li2Al4B6O20The crucible of the mixture that F raw materials of compound is mixed is placed in crystal In growth furnace, more than 750 DEG C are slowly warmed up to, are incubated more than 12 hours, then slow cooling spontaneous crystallization is obtained K3Sr3Li2Al4B6O20F crystal.
Described flux is Li2O、SrF2And H3BO3It is 6 according to mol ratio:1.5:8 mix.
Embodiment 7
Using the described K of flux growth metrhod growth3Sr3Li2Al4B6O20F nonlinear optical crystals, comprise the following steps：
It is 10.5 by mol ratio:1 flux and described K3Sr3Li2Al4B6O20F raw materials of compound is put into crucible, Stir, will then fill flux and K3Sr3Li2Al4B6O20The crucible of the mixture that F raw materials of compound is mixed is put In crystal growing furnace, more than 750 DEG C are slowly warmed up to, are incubated more than 12 hours, then slow cooling spontaneous crystallization is obtained K3Sr3Li2Al4B6O20F crystal.
Described flux is Li2O、SrF2And H3BO3It is 4 according to mol ratio:1:5 mix.
Embodiment 8
Using the described K of flux growth metrhod growth3Sr3Li2Al4B6O20F nonlinear optical crystals, comprise the following steps：
It is 11.5 by mol ratio:1 flux and described K3Sr3Li2Al4B6O20F raw materials of compound is put into crucible, Stir, will then fill flux and K3Sr3Li2Al4B6O20The crucible of the mixture that F raw materials of compound is mixed is put In crystal growing furnace, more than 750 DEG C are slowly warmed up to, are incubated more than 12 hours, then slow cooling spontaneous crystallization is obtained K3Sr3Li2Al4B6O20F crystal.
Described flux is Li2O、SrF2And H3BO3It is 3 according to mol ratio:1:6 mix.
Embodiment 9
After tested, the K prepared by embodiment 5-83Sr3Li2Al4B6O20F nonlinear optical crystals are free of symmetrical centre, category In trigonal system R32 space groups, cell parameter is α=90.00, β=90.00, γ=120.00, V=1532.59 (12)3, Z=3.With again Frequency effect；Fig. 3 is the K3Sr3Li2Al4B6O20The structural representation of F nonlinear optical crystals.
Embodiment 10
By the K of the gained of embodiment 73Sr3Li2Al4B6O20F nonlinear optical crystals make diffuse reflectance spectroscopy, the crystal UV absorption cut-off side is less than 200nm, and is passed through in 200-1100nm wave-length coverages；The crystal is not easily broken, it is easy to cut Cut and polishing；By the K of the gained of embodiment 73Sr3Li2Al4B6O20F nonlinear optical crystals, are placed on the shown device mark of accompanying drawing 1 At number for 3 position, at room temperature, with adjusting Q Nd:YAG laser makees fundamental frequency light source, and incident wavelength is the near-infrared of 1064nm Light, output wavelength is the green laser of 532nm, and laser intensity is approximately equivalent to KH2PO4(KDP) 0.9 times.
Accompanying drawing 1 is to use K to the present invention3Sr3Li2Al4B6O20The simple declaration of the device for non-linear optical that F crystal makes. Light beam 2 is sent by laser 1 and injects K3Sr3Li2Al4B6O20F crystal 3, produced outgoing beam 4 passes through filter plate 5, so that Laser beam required for obtaining.The nonlinear optics laser can be times frequency generator or upper and lower frequency converter or beche-de-mer without spike Amount oscillator etc..
Above-mentioned specific embodiment is that technical scheme is explained in detail, the present invention not only only office Be limited to above-described embodiment, it will be understood by those skilled in the art that it is every according to above-mentioned principle and spirit on the basis of the present invention Improve, substitute, all should be within protection scope of the present invention.

Claims (9)

1.K3Sr3Li2Al4B6O20F compounds, it is characterised in that：Described K3Sr3Li2Al4B6O20The chemical formula of F compounds is K3Sr3Li2Al4B6O20F。
2.K3Sr3Li2Al4B6O20F nonlinear optical crystals, it is characterised in that：Described K3Sr3Li2Al4B6O20F nonlinear opticses Crystal is free of symmetrical centre, belongs to the space groups of trigonal system R 32.
3. K according to claim 23Sr3Li2Al4B6O20F nonlinear optical crystals, it is characterised in that：Described K3Sr3Li2Al4B6O20The cell parameter of F nonlinear optical crystals is α=90.00, β=90.00, γ=120.00, V=1532.59 (12)3, Z=3.
4. the K according to Claims 2 or 33Sr3Li2Al4B6O20The preparation method of F nonlinear optical crystals, its feature exists In：Comprise the following steps：
K compounds, compound containing Sr, compound containing Li, compound containing Al, boride alloy and compound containing F will be contained in terms of chemistry After amount is than uniform mixing, 450-650 DEG C is warmed up to 10-200 DEG C/h of speed, then heat preservation sintering more than 12 hours, dropped Grinding is taken out after to room temperature uniform, then 600-800 DEG C is warmed up to 10-200 DEG C/h of speed and sintered more than 24 hours, in Grinding more than 1 time is taken out on way, obtains final product described K3Sr3Li2Al4B6O20F nonlinear optical crystals.
5. K according to claim 43Sr3Li2Al4B6O20The preparation method of F nonlinear optical crystals, it is characterised in that：Institute Compound containing K is stated for K2CO3、KNO3Or KHCO3；The compound containing Sr is SrCO3、Sr(OH)2Or Sr (NO3)2；It is described containing Li Compound is Li2CO3Or LiOHH2O；The compound containing Al is Al2O3；The boride alloy is H3BO3；It is described containing Fization Compound is LiF, KBF4, KF or SrF2。
6. K according to claim 43Sr3Li2Al4B6O20The preparation method of F nonlinear optical crystals：Also include following step Suddenly：
It is 7.5~15.5 by mol ratio:1 flux and described K3Sr3Li2Al4B6O20F nonlinear optical crystals are put into crucible It is interior, stir, then crucible is placed in crystal growing furnace, more than 750 DEG C are slowly warmed up to, more than 12 hours are incubated, so Slow cooling spontaneous crystallization afterwards obtains larger-sized K3Sr3Li2Al4B6O20F crystal.
7. K according to claim 63Sr3Li2Al4B6O20The preparation method of F nonlinear optical crystals：Described flux By Li2O、SrF2And H3BO3It is 3~6 according to mol ratio:0.5~1.5:4~8 mix.
8. the K according to Claims 2 or 33Sr3Li2Al4B6O20The purposes of F nonlinear optical crystals, it is characterised in that institute The K for stating3Sr3Li2Al4B6O20F nonlinear optical crystals are used as device for non-linear optical.
9. a kind of device for non-linear optical, its feature is：Including the K according to Claims 2 or 33Sr3Li2Al4B6O20F Nonlinear optical crystal.
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