CN104562203A - Compound lithium rubidium borate non-linear optical crystal as well as preparation method and application thereof - Google Patents

Compound lithium rubidium borate non-linear optical crystal as well as preparation method and application thereof Download PDF

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CN104562203A
CN104562203A CN201310509439.2A CN201310509439A CN104562203A CN 104562203 A CN104562203 A CN 104562203A CN 201310509439 A CN201310509439 A CN 201310509439A CN 104562203 A CN104562203 A CN 104562203A
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crystal
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seed
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rubidium
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潘世烈
杨云
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Xinjiang Technical Institute of Physics and Chemistry 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
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
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    • 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
    • G02F1/353—Frequency conversion, i.e. wherein a light beam is generated with frequency components different from those of the incident light beams
    • 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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  • Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)

Abstract

The invention relates to a compound lithium rubidium borate non-linear optical crystal as well as a preparation method and application thereof. A chemical formula of the crystal is Li4Rb3B7O14, the molecular weight of the crystal is 583.84, the crystal belongs to a trigonal crystal system and a space group P3121, lattice parameters of the crystal are that a is equal to 6.8765(5) angstroms, b is equal to 6.8765(5) angstroms, c is equal to 25.923(4) angstroms, Z is equal to 3 and V is equal to 1061.56(19) angstroms, and the Moh's hardness is 2-3. Crystal growth is performed by adopting a flux growth method, and the crystal disclosed by the invention has a large size with at least centimeter levels; and the crystal has the advantages of high preparation speed, simplicity in operation, low cost, large prepared crystal size, wide light-permeable wave band, good mechanical performance, difficulty in breaking, stable physical and chemical properties, easiness in processing and the like, is suitable for the needs of laser frequency conversion of ultraviolet wave bands, and can be used for preparing non-linear optical devices.

Description

Boronic acid compound lithium rubidium non-linear optic crystal and its production and use
Technical field
The present invention relates to a kind of boronic acid compound lithium rubidium non-linear optic crystal and its production and use, the chemical formula of this crystal is Li 4rb 3b 7o 14.
Background technology
Non-linear optical crystal material is one of important photoelectric information functional material, be photoelectron technology particularly laser technology important substance basis, be with a wide range of applications and huge using value in the field such as information, the energy, industry manufacture, medical science, military affairs, promoted the fast development of laser in socio-economic development and national security.Because borate nonlinear optical crystal is current application laser frequency doubling crystal widely as important double-frequency material, in borate salt system, explore novel nonlinear optical crystal and the high-level efficiency realizing optical maser wavelength is converted into the focus that laser field is paid close attention to always.
Solid laser utilizes non-linear optic crystal can export the LASER Light Source of ultraviolet band (λ <400nm) by frequency inverted, and this is also the most effective and the most direct method that can obtain high-power ultraviolet laser light output.And the strong coherent laser light source of 355nm is the wave band of the laser frequency that scientists both domestic and external is all paid much attention to and paid close attention in ultraviolet band.This is that energy is more concentrated due to 355nm Ultra-Violet Laser because wavelength is short, and resolving power is higher, has important application at the industrial circles such as high density compact disc storage, material surface modification, laser precision machining and the medical field such as ultraviolet radiography, cell parsing.355nm ultraviolet laser beams can as the write light source of forth generation CD, also can be used for ionization, decomposition compound, interrupt corresponding chemical bond in compound (this is because the chemical bond of a lot of compound, biomolecules all ruptures near 355nm), if break through the application of these wave length laser beams, the development that it will not drive the subjects such as laser chemistry, Ultra-Violet Laser spectroscopy and laser medicine at full speed.And be conducive to promoting the national economic development, solve the key technical problem relating to the photoelectric functional material of national long term growth and national security.
β-BaB 2o 4(BBO) be Chinese Academy of Sciences's Fujian thing structure in 1985 the non-linear optic crystal with significant application value of Late Cambrian in the world, be widely used in Nd:YAG laser apparatus two, three, four, fifth harmonic exports.After BBO, Wu in 1989 to become to wait people from the relation of crystalline structure with performance, in the research to borate series compound with find a kind of new ultra-violet frequency-doubling crystal LiB in screening 3o 5(LBO).LBO has larger Clock Multiplier Factor, wide through wave band (ultraviolet cut-on wavelength reaches 155nm), high light injury threshold, can realize 90 ° and non-critically to match, and has been widely used in two of superpower Nd:YAG laser apparatus at present, on frequency tripling and photoparametric amplifier.Chinese Academy of Sciences's nineties in last century Fujian thing structure successfully have developed KBe 2(BO 3) F 2(KBBF) deep ultraviolet nonlinear optical crystal, this crystal is the double-frequency material that uniquely can realize the output of 177.3nm wavelength at present.KBBF group crystal is that China is in non-linear optic crystal research field, the 3rd China card non-linear optic crystal after the existing BBO of secondary, lbo crystal, have ground-breaking effect to the development and application that promote all-solid-state deep ultraviolet laser source, also sufficient proof China continues in non-linear optic crystal field to keep the leading level in the world.Although existing non-linear optic crystal such as BBO, LBO, KBBF are widely used, along with the development of society, the demand of the mankind to technology is endless.Therefore, the important topic that high performance novel nonlinear optical crystal material is photoelectric functional material field is explored.
Patent related to the present invention and article have:
1, di lithium tetra borate rubidium nonlinear optic crystal and its production and use, the patent No.: 201010553379.0, Pan Shilie, Yang Yun; That involved is Li 6rb 5b 11o 22crystal.This Li 6rb 5b 11o 22crystal is a kind of novel non-linear optic crystal being expected to be used in ultraviolet band.This crystal is folk prescription crystallographic system, spacer C2, molecular weight 939.90, and unit cell parameters is a=11.6252 (5), b=7.1010 (3), z=2.Li 6rb 5b 11o 224liO is comprised in crystalline structure n(n=4,5) group, RbO n(n=9,10) group and independently B 11o 22group.These three kinds of groups tie up network structures by three complexity that are connected to form sharing Sauerstoffatom.This B independently containing 11 boron 11o 22find in any report that group is not former, 11:[2 (5:3 Δ+2T)+(1 Δ) can be defined as].By the test of compound ultraviolet face reflection collection of illustrative plates, its ultraviolet absorption edge is 190nm, its non-linear optical effect and 2/3KH 2pO 4(KDP) suitable.
2, boronic acid compound lithium rubidium non-linear optic crystal and its production and use, the patent No.: Pan 201110122428.X generation is strong, Yang Yun; That involved is Li 5rb 2b 7o 14crystal.This Li 5rb 2b 7o 14crystal belongs to rhombic system, and point group is mm2, and spacer is Ama2, and unit cell parameters is: z=2, crystal analysis result and infrared spectra all confirm, containing BO in structure 3and BO 4group.Li 5rb 2b 7o 14liO is comprised in crystalline structure n(n=4,5,6) group, RbO 10structural unit basic in group and independently crystalline structure is two kinds of different 1D B-O chains.These three kinds of groups are by sharing the three-dimensional net structure being connected to form complexity of Sauerstoffatom.By the test of compound ultraviolet face reflection collection of illustrative plates, its ultraviolet absorption edge is 190nm, and powder SHG effect is approximately 0.5 times of KDP.
Summary of the invention:
The object of the invention is, for solving the needs being applied to the nonlinear optical material of all solid state ultraviolet/deep ultraviolet laser system, provide a kind of boronic acid compound lithium rubidium non-linear optic crystal, the chemical formula of this crystal is Li 4rb 3b 7o 14, molecular weight 583.84, belongs to trigonal system, spacer P3 121, unit cell parameters is z=3, mohs' hardness is 2-3.
Another object of the present invention provides compound L i 4rb 3b 7o 14the preparation method of crystal.
Another object of the present invention is to provide uses Li 4rb 3b 7o 14the purposes of crystal preparation device for non-linear optical.
A kind of boronic acid compound lithium rubidium non-linear optic crystal of the present invention, the chemical formula of this crystal is Li 4rb 3b 7o 14, molecular weight 583.84, spacer is P3 121, unit cell parameters is z=3, mohs' hardness is 2-3.
The preparation method of described boronic acid compound lithium rubidium non-linear optic crystal, adopt flux method growing crystal, concrete operation step is pressed and is carried out:
A, by compound L i 4rb 3b 7o 14in add fusing assistant Rb 2o, Rb 2cO 3, RbNO 3, Rb 2c 2o 4h 2o, RbOH or RbC 2h 3o 2, be heated to 700-1000 DEG C, then be cooled to 555-620 DEG C, obtain Li 4rb 3b 7o 14with the blend melt of fusing assistant;
B, with the speed slow cooling of 0.5-10 DEG C/h to room temperature, crystallization obtain seed crystal or use in cooling platinum filament suspension method obtain small-crystalline as seed crystal;
C, at compound L i 4rb 3b 7o 14with growing crystal in the blend melt of fusing assistant surface or blend melt: by the seed crystal that is fixed on seed rod from seed crystal crystal growing furnace top, make seed crystal and step a blend melt surface contact or stretch in blend melt, be cooled to 550-560 DEG C, then rotate seed crystal or crucible with the rotating speed of 0-100rpm;
D, to arrive after required yardstick until single crystal growing, make crystal depart from melt liquid level, be down to room temperature with the speed of temperature 1-100 DEG C/h, then slowly from burner hearth, take out crystal; Di lithium tetra borate rubidium nonlinear optic crystal can be obtained.
Compound containing lithium in boronic acid compound lithium rubidium described in step a is Li 2o, LiNO 3, LiOH, Li 2cO 3, LiC 2h 3o 2, Li 2c 2o 4h 2o, LiF or LiCl; Compound containing rubidium is Rb 2o, Rb 2cO 3, RbNO 3, Rb 2c 2o 4h 2o, RbOH, RbC 2h 3o 2, RbF or RbCl; Boron-containing compound is H 3bO 3or B 2o 3.
Li in step a 4rb 3b 7o 14be 1:0.1-3 with the mol ratio of solubility promoter.
Described compound L i 4rb 3b 7o 14non-linear optic crystal is in the purposes of preparation times frequency generator, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
Described times of frequency generator, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator comprise at least a branch of incidence electromagnetic radiation is different from the output radiation of incidence electromagnetic radiation device by producing at least a branch of frequency after at least one block of non-linear optic crystal.
Compound L i of the present invention 4rb 3b 7o 14non-linear optic crystal, this crystal has following characteristics in preparation process:
There is provided and use flux method to prepare Li 4rb 3b 7o 14the method of non-linear optic crystal adopts compound flux method growing crystal, puts into configure and pretreated raw material and fusing assistant mix in proportion, wherein Li in crucible 4rb 3b 7o 14be 1:0.1-3 with the mol ratio of solubility promoter, by the mixture melt of this raw material and fusing assistant, growing crystal in blend melt surface or blend melt.Concrete steps are as follows:
First by Li 4rb 3b 7o 14compound and fusing assistant mix in proportion and be heated to fusing in crucibles, or add fusing assistant preparing lithium tetraborate rubidium compound simultaneously, mix in proportion, fusing is heated in crucible, and at the temperature 1-100h higher than fusing point, be cooled to the temperature higher than fusing point 0-10 DEG C again, obtain the mixed molten liquid of boronic acid containing lithium rubidium and fusing assistant, stand-by; Using the speed slow cooling of 0.5-10 DEG C/h to room temperature spontaneous crystallization or use platinum filament suspension method to obtain small-crystalline as seed crystal, or process is carried out to existing crystal boule obtain seed crystal;
Growing crystal in the blend melt of compound and fusing assistant: comprise with seeded growth, with during seed crystal, seed crystal is fixed on seed rod, from top, seed crystal and compound and fusing assistant blend melt surface contact, be cooled to temperature of saturation; Or the compound fusing assistant blend melt directly will prepared in crucible, be cooled to temperature of saturation; Seed crystal and/or crucible is rotated with the rotating speed of 0 ~ 100rpm; After single crystal growing to required yardstick, make crystal depart from melt liquid level, be down to room temperature with the speed of temperature 100 DEG C/h, the Li then will prepared 4rb 3b 7o 14non-linear optic crystal slowly takes out from burner hearth.
In principle, with above-mentioned system, general chemical synthesis process is adopted to prepare Li 4rb 3b 7o 14polycrystal raw material; Preferred solid reaction process, that is:, after being mixed by the raw materials of compound containing Li, Rb and B mol ratio being 4:3:7, solid state reaction is carried out in heating, and can obtain chemical formula is Li 4rb 3b 7o 14compound.
Preparation Li 4rb 3b 7o 14the chemical equation of compound:
（1）Li 2O+H 3BO 3+Rb 2O→Li 4Rb 3B 7O 14+H 2O↑；
（2）Li 2CO 3+B 2O 3+Rb 2CO 3→Li 4Rb 3B 7O 14+CO 2↑；
（3）LiNO 3+B 2O 3+Rb 2CO 3→Li 4Rb 3B 7O 14+NO 2↑+O 2↑；
（4）LiOH+H 3BO 3+Rb 2O→Li 4Rb 3B 7O 14+H 2O↑；
（5）LiCH 3COO·nH 2O+B 2O 3+Rb 2CO 3+O 2→Li 4Rb 3B 7O 14+CO 2↑+H 2O↑；
（6）Li 2C 2O 4·nH 2O+H 3BO 3+Rb 2O+O 2→Li 4Rb 3B 7O 14+CO 2↑+H 2O↑；
（7）LiCl+B 2O 3+Rb 2O+O 2→Li 4Rb 3B 7O 14+Cl 2↑+H 2O↑。
Contain Li in the present invention, commercially available reagent and raw material can be adopted containing Rb and boride alloy.
Large size Li prepared by the present invention 4rb 3b 7o 14non-linear optic crystal, as preparing device for non-linear optical, comprises and makes times frequency generator, upper or lower frequency transmodulator and optical parametric oscillator.Described uses Li 4rb 3b 7o 14the nonlinear device that non-linear optic crystal makes comprises the coherent light by being different from incident light through at least a branch of frequency of at least a branch of incident fundamental wave generation.
Described Li 4rb 3b 7o 14non-linear optic crystal to optical manufacturing precision without particular requirement.
The invention provides and adopt flux method growth method to prepare Li 4rb 3b 7o 14non-linear optic crystal and with Li 4rb 3b 7o 14the device for non-linear optical that crystal makes.Preparation method of the present invention is compared with the existing non-linear optic crystal technology of preparing being applied to ultraviolet/deep UV (ultraviolet light) wave band frequency conversion, crystal is very easily grown up and transparent in inclusion, has simple to operate, fast growth, cost is low, easily obtains the advantages such as large-size crystal.
That the present invention relates to is Li 4rb 3b 7o 14crystal.The molecular weight 583.84 of this crystal, belongs to trigonal system, spacer P3 121, unit cell parameters is z=3, mohs' hardness is 2-3.Cross the test of parsing to compound monocrystal structure and ultimate analysis and other performances, determine crystalline structure and molecular formula.This crystal is three-dimensional net structure in space, containing LiO in molecule n(n=4,5) group, RbO n(n=9,10) group and independently B 7o 14group.By the test of compound ultraviolet face reflection collection of illustrative plates, its ultraviolet absorption edge is 190nm, its non-linear optical effect and 0.5KH 2pO 4(KDP) suitable.
Accompanying drawing explanation
Fig. 1 is Li of the present invention 4rb 3b 7o 14powder x-ray diffraction collection of illustrative plates;
Fig. 2 is Li of the present invention 4rb 3b 7o 14single crystal structure figure;
Fig. 3 is Li of the present invention 4rb 3b 7o 14monocrystalline figure;
Fig. 4 is Li of the present invention 4rb 3b 7o 14the fundamental diagram of the device for non-linear optical that crystal makes, wherein: (1) is laser apparatus, (2) are light beam, and (3) are crystal, and (4) are outgoing beam, and (5) are filter plate; Send light beam 2 by laser apparatus 1 and inject large size Li 4rb 3b 7o 14non-linear optic crystal 3, the outgoing beam 4 produced is by filter plate 5, thus the laser beam required for obtaining.Laser apparatus 1 can be neodymium-doped yttrium-aluminum garnet (Nd:YAG) laser apparatus or other laser apparatus, and concerning the frequency doubling device using Nd:YAG laser light source, the infrared light of incoming beam 2 to be wavelength be 1064nm, passes through Li 4rb 3b 7o 14monocrystalline produces the green frequency doubled light that wavelength is 532nm, and outgoing beam 4 is the infrared light of 1064nm and the green glow of 532nm containing wavelength, and the effect of filter plate 5 is elimination infrared light compositions, only allows green frequency doubled light to pass through.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail, but be not limited only to embodiments of the invention;
Embodiment 1:
Synthesis Li 4rb 3b 7o 14compound:
Adopt solid state synthesis method to sinter at high temperature 550 DEG C, its chemical equation is: Li 2cO 3+ B 2o 3+ Rb 2cO 3→ Li 4rb 3b 7o 14+ NO 2↑+O 2↑;
By Li 2cO 3, H 3bO 3, Rb 2cO 3stoichiometrically than putting into mortar, mixing is also carefully ground, and then loads in the opening corundum crucible of Φ 100mm × 100mm, compressed, put into retort furnace, be slowly warming up to 450 DEG C, constant temperature 5 hours, gas is driven out of as far as possible, take out crucible after cooling, take out sample and again grind evenly, be placed in crucible again, in 550 DEG C of constant temperature 48 hours again in muffle furnace, taken out, put into mortar and smash grinding to pieces and namely obtain compound L i 4rb 3b 7o 14, X-ray analysis is carried out to this product, gained X-ray spectrogram and finished product Li 4rb 3b 7o 14monocrystalline last X-ray spectrogram of pulverizing is consistent;
By the compound L i of synthesis 4rb 3b 7o 14with fusing assistant Rb 2cO 3li in molar ratio 4rb 3b 7o 14: Rb 2cO 3=1:0.5 loads in the opening platinum crucible of Φ 80mm × 80mm, and crucible is put into crystal growing furnace, is warming up to 750 DEG C, constant temperature, after 30 hours, is cooled to 610 DEG C, obtains Li 4rb 3b 7o 14with the blend melt of fusing assistant;
With the speed slow cooling of temperature 0.5 DEG C/h to room temperature, crystallization obtains seed crystal;
At compound L i 4rb 3b 7o 14with the blend melt surface growth crystal of fusing assistant: will the Li of seed rod lower end be fixed on 4rb 3b 7o 14seed crystal imports crucible from furnace roof portion aperture, seed crystal is contacted with melt liquid level, is cooled to 560 DEG C, then with 50rpm rotating speed rotary seed crystal rod;
Arrive after required yardstick until single crystal growing, make crystal depart from melt liquid level, be down to room temperature with the speed of temperature 80 DEG C/h, then from burner hearth, take out crystal lentamente, obtain be of a size of 30mm × 25mm × 10mm can obtain lithium tetraborate rubidium Li 4rb 3b 7o 14non-linear optic crystal.
By method described in embodiment 1, by reaction formula Li 2o+B 2o 3+ Rb 2o+O 2→ Li 4rb 3b 7o 14+ Cl 2↑+H 2o ↑ synthesis Li 4rb 3b 7o 14compound, also can obtain Li 4rb 3b 7o 14crystal.
Embodiment 2:
By reaction formula Li 2cO 3+ B 2o 3+ Rb 2o → Li 4rb 3b 7o 14+ CO 2↑ synthetic compound Li 4rb 3b 7o 14, concrete operation step carries out according to embodiment 1;
By the compound L i of synthesis 4rb 3b 7o 14with fusing assistant Rb 2cO 3li in molar ratio 4rb 3b 7o 14: Rb 2cO 3=1:1 puts into the opening platinum crucible of Φ 100mm × 100mm, and crucible is put into crystal growing furnace, is warming up to 700 DEG C, and constant temperature, after 80 hours, is cooled to 555 DEG C, obtains Li 4rb 3b 7o 14with the blend melt of fusing assistant;
With the speed slow cooling of temperature 1 DEG C/h to room temperature, in cooling, platinum filament suspension method is used to obtain small-crystalline as seed crystal;
At compound L i 4rb 3b 7o 14with growing crystal in the blend melt of fusing assistant: by the Li cut along arbitrary axis 4rb 3b 7o 14seed crystal platinum filament is fixed on seed rod lower end, from furnace roof portion aperture, seed crystal is imported crucible, seed crystal is immersed in melt, is cooled to 550 DEG C, then rotate seed crystal crucible with the rotating speed of 70rpm;
Arrive after required yardstick until single crystal growing, by crystal lift-off melt liquid level, be down to room temperature with the speed of temperature 20 DEG C/h, then from burner hearth, take out crystal lentamente, obtain the lithium tetraborate rubidium Li being of a size of 18mm × 18mm × 17mm 4rb 3b 7o 14non-linear optic crystal.
By method described in embodiment 2, reaction formula Rb 2cO 3+ B 2o 3+ Li 2cO 3→ Li 4rb 3b 7o 14+ CO 2↑ synthesis Li 4rb 3b 7o 14compound, also can obtain Li 4rb 3b 7o 14monocrystalline.
Embodiment 3:
By reaction formula LiOH+H 3bO 3+ RbOH → Li 4rb 3b 7o 14+ H 2o ↑ synthetic compound Li 4rb 3b 7o 14, concrete operation step carries out according to embodiment 1;
By the compound L i of synthesis 4rb 3b 7o 14with fusing assistant Rb 2o is Li in molar ratio 4rb 3b 7o 14: Rb 2o=1:0.5 puts into the opening platinum crucible of Φ 100mm × 100mm, and crucible is put into crystal growing furnace, is warming up to 1000 DEG C, and constant temperature, after 20 hours, is cooled to 580 DEG C, obtains Li 4rb 3b 7o 14with the blend melt of fusing assistant;
With the speed slow cooling of temperature 3 DEG C/h to room temperature, in cooling, platinum filament suspension method is used to obtain small-crystalline as seed crystal;
At compound L i 4rb 3b 7o 14with growing crystal in the blend melt surface of fusing assistant: by the Li cut along c-axis 4rb 3b 7o 14seed crystal platinum filament is fixed on seed rod lower end, from furnace roof portion aperture, seed crystal is imported crucible, seed crystal is contacted with melt liquid level, be cooled to 555 DEG C, then with the rotating speed rotary seed crystal rod of 20rpm;
Arrive after required yardstick until single crystal growing, make crystal depart from melt liquid level, be down to room temperature with the speed of temperature 40 DEG C/h, then from burner hearth, take out crystal lentamente, obtain the lithium tetraborate rubidium Li being of a size of 65mm × 65mm × 15mm 4rb 3b 7o 14non-linear optic crystal.
By method described in embodiment 3, by reaction formula Li 2o+H 3bO 3+ Rb 2o → Li 4rb 3b 7o 14+ H 2o ↑ synthesis Li 4rb 3b 7o 14compound, also can obtain Li 4rb 3b 7o 14monocrystalline.
Embodiment 4:
By reaction formula LiOH+H 3bO 3+ RbOH → Li 4rb 3b 7o 14+ H 2o ↑ synthesis Li 4rb 3b 7o 14compound, concrete operation step carries out according to embodiment 1;
By the compound L i of synthesis 4rb 3b 7o 14with fusing assistant RbOH Li in molar ratio 4rb 3b 7o 14: RbOH=1:1 puts into the opening platinum crucible of Φ 100mm × 100mm, and crucible is put into crystal growing furnace, is warming up to 700 DEG C, and constant temperature, after 40 hours, is cooled to 560 DEG C, obtains Li 4rb 3b 7o 14with the blend melt of fusing assistant;
With the speed slow cooling of temperature 5 DEG C/h to room temperature, in cooling, platinum filament suspension method is used to obtain small-crystalline as seed crystal;
At compound L i 4rb 3b 7o 14with growing crystal in the blend melt of fusing assistant: by the Li cut along arbitrary axis 4rb 3b 7o 14seed crystal platinum filament is fixed on seed rod lower end, from furnace roof portion aperture, seed crystal is imported crucible, and seed crystal is immersed in melt, and be cooled to 558 DEG C, seed rod speed of rotation is 0(non rotating);
Arrive after required yardstick until single crystal growing, make crystal lift-off melt liquid level, be down to room temperature with the speed of temperature 50 C/h, then from burner hearth, take out crystal lentamente, obtain the lithium tetraborate rubidium Li being of a size of Φ 37mm × 37mm × 15mm 4rb 3b 7o 14non-linear optic crystal.
By method described in embodiment 4, by reaction formula LiNO 3+ B 2o 3+ RbNO 3→ Li 4rb 3b 7o 14+ NO 2↑+O 2↑ synthesis Li 4rb 3b 7o 14compound, also can obtain Li 4rb 3b 7o 14monocrystalline.
Embodiment 5:
By reaction formula LiNO 3+ B 2o 3+ RbNO 3→ Li 4rb 3b 7o 14+ NO 2↑+O 2↑ synthesis Li 4rb 3b 7o 14compound, concrete operation step carries out according to embodiment 1;
By the Li of synthesis 4rb 3b 7o 14compound and fusing assistant Rb 2cO 3li in molar ratio 4rb 3b 7o 14: Rb 2cO 3=1:1 loads in the opening platinum crucible of Φ 150mm × 150mm, and be warming up to 800 DEG C, constant temperature was cooled to 570 DEG C after 50 hours, obtained Li 4rb 3b 7o 14with the blend melt of fusing assistant;
With the speed slow cooling of temperature 8 DEG C/h to room temperature, in cooling, platinum filament suspension method is used to obtain small-crystalline as seed crystal;
At compound L i 4rb 3b 7o 14with the blend melt surface growth crystal of fusing assistant: by the Li cut along arbitrary axis 4rb 3b 7o 14seed crystal platinum filament is fixed on seed rod lower end, from furnace roof portion aperture, seed crystal is imported crucible, makes it to contact with liquid level, then rotates seed crystal with the rotating speed of 15rpm, constant temperature 1 hour, fast cooling to 553 DEG C;
Arrive after required yardstick until single crystal growing, make crystal depart from liquid level, be down to room temperature with temperature 70 C/hour speed, then slowly from burner hearth, take out crystal, obtain the transparent lithium tetraborate rubidium Li being of a size of 60mm × 60mm × 20mm 4rb 3b 7o 14non-linear optic crystal.
By method described in embodiment 5, by reaction formula Li 2c 2o 4nH 2o+H 3bO 3+ Rb 2c 2o 4nH 2o+O 2→ Li 4rb 3b 7o 14+ CO 2↑+H 2o ↑ synthesis Li 4rb 3b 7o 14compound, also can obtain Li 4rb 3b 7o 14monocrystalline.
Embodiment 6:
By reaction formula Li 2cO 3+ B 2o 3+ Rb 2o → Li 4rb 3b 7o 14+ CO 2↑ synthesis Li 4rb 3b 7o 14compound, concrete operation step carries out according to embodiment 1;
By the Li of synthesis 4rb 3b 7o 14compound and fusing assistant Rb 2cO 3li in molar ratio 4rb 3b 7o 14: Rb 2cO 3=1:2 enters in the opening platinum crucible of Φ 100mm × 100mm, is warming up to 800 DEG C, and constant temperature was cooled to 565 DEG C after 1 hour, obtained Li 4rb 3b 7o 14with the blend melt of fusing assistant;
With the speed slow cooling of temperature 10 DEG C/h to room temperature, in cooling, platinum filament suspension method is used to obtain small-crystalline as seed crystal;
At compound L i 4rb 3b 7o 14with the blend melt surface growth crystal of fusing assistant: by the Li cut along arbitrary axis 4rb 3b 7o 14seed crystal platinum filament is fixed on seed rod lower end, from furnace roof portion aperture, seed crystal is imported crucible, makes it to contact with liquid level, is cooled to 550 DEG C, then rotates seed crystal with the rotating speed of 85rpm;
Arrive after required yardstick until single crystal growing, make crystal depart from liquid level, be down to room temperature with temperature 10 DEG C/h of speed, then slowly from burner hearth, take out crystal, obtain the transparent lithium tetraborate rubidium Li being of a size of 45mm × 50mm × 14mm 4rb 3b 7o 14non-linear optic crystal.
By method described in embodiment 6, by reaction formula Li 2c 2o 42H 2o+H 3bO 3+ Rb 2c 2o 4nH 2o+O 2→ Li 4rb 3b 7o 14+ CO 2↑+H 2o ↑ synthesis Li 4rb 3b 7o 14compound 0, also can obtain Li 4rb 3b 7o 14monocrystalline.
Embodiment 7:
By reaction formula LiCl+B 2o 3+ RbOH+O 2→ Li 4rb 3b 7o 14+ Cl 2↑+H 2o ↑ one-tenth Li 4rb 3b 7o 14compound, concrete operation step carries out according to embodiment 1;
By the Li of synthesis 4rb 3b 7o 14compound and fusing assistant Rb 2o is Li in molar ratio 4rb 3b 7o 14: Rb 2o=1:0.5 loads in the opening platinum crucible of Φ 100mm × 100mm, and be warming up to 800 DEG C, constant temperature was cooled to 620 DEG C after 100 hours, obtained Li 4rb 3b 7o 14with the blend melt of fusing assistant;
With the speed slow cooling of temperature 0.5 DEG C/h to room temperature, in cooling, platinum filament suspension method is used to obtain small-crystalline as seed crystal;
At compound L i 4rb 3b 7o 14with growing crystal in the blend melt of fusing assistant: by the Li cut along c-axis 4rb 3b 7o 14seed crystal platinum filament is fixed on seed rod lower end, from furnace roof portion aperture, seed crystal is imported crucible, under immersed in liquid level, then rotate seed crystal seed crystal with the rotating speed of 10rpm, constant temperature 0.5 hour, fast cooling to 556 DEG C, arrive after required yardstick until single crystal growing, make crystal depart from liquid level, be down to room temperature with temperature 100 DEG C/h of speed, then slowly from burner hearth, take out crystal, obtain the transparent lithium tetraborate rubidium Li being of a size of 50mm × 70mm × 15mm 4rb 3b 7o 14non-linear optic crystal.
By method described in embodiment 7, by reaction formula Li 2o+B 2o 3+ Rb 2o → Li 4rb 3b 7o 14+ H 2o ↑ synthesis Li 4rb 3b 7o 14compound, also can obtain Li 4rb 3b 7o 14monocrystalline.
Embodiment 8:
By reaction formula Li 2c 2o 4nH 2o+H 3bO 3+ Rb 2c 2o 4nH 2o+O 2→ Li 4rb 3b 7o 14+ CO 2↑+H 2o ↑ synthesis Li 4rb 3b 7o 14compound, concrete operation step carries out according to embodiment 1;
By the Li of synthesis 4rb 3b 7o 14compound and fusing assistant RbOH Li in molar ratio 4rb 3b 7o 14: RbOH=1:3 puts into the opening platinum crucible of Φ 80mm × 80mm, and crucible is put into crystal growing furnace, is warming up to 700 DEG C, and constant temperature, after 1 hour, is cooled to 550 DEG C, obtains Li 4rb 3b 7o 14with the blend melt of fusing assistant;
With the speed slow cooling of temperature 4 DEG C/h to room temperature, in cooling, platinum filament suspension method is used to obtain small-crystalline as seed crystal;
At compound L i 4rb 3b 7o 14with the blend melt surface growth crystal of fusing assistant: by the Li cut along arbitrary axis 4rb 3b 7o 14seed crystal platinum filament is fixed on seed rod lower end, from furnace roof portion aperture, seed crystal is imported crucible, seed crystal is contacted with melt liquid level, then rotates seed crystal with the rotating speed of 100rpm;
Arrive after required yardstick until single crystal growing, by crystal lift-off melt liquid level, be down to room temperature with the speed of temperature 100 DEG C/h, then from burner hearth, take out crystal lentamente, obtain the lithium tetraborate rubidium Li being of a size of Φ 32mm × 32mm × 25mm 4rb 3b 7o 14non-linear optic crystal.
By method described in embodiment 8, by reaction formula LiCH 3cOOnH 2o+B 2o 3+ Rb 2cO 3+ O 2→ Li 4rb 3b 7o 14+ CO 2↑+H 2o ↑ synthesis Li 4rb 3b 7o 14compound.
Embodiment 9:
By any one Li of embodiment 1-8 gained 4rb 3b 7o 14crystal, the frequency doubling device of one piece of size 4mm × 4mm × 8mm is processed by the direction that matches, be placed on the position of 3 by shown in accompanying drawing 3, at room temperature, with tune Q Nd:YAG laser light source, incident wavelength is 1064nm, and sending wavelength by adjusting Q Nd:YAG laser apparatus 1 is that Li injected by the infrared beam 2 of 1064nm 4rb 3b 7o 14single crystal 3, produce the green frequency doubled light that wavelength is 532nm, outgoing beam 4 is the infrared light of 1064nm and the green glow of 532nm containing wavelength, and filter plate 5 elimination infrared light composition, obtains the green laser that wavelength is 532nm.

Claims (5)

1. a boronic acid compound lithium rubidium non-linear optic crystal, is characterized in that the chemical formula of this crystal is Li 4rb 3b 7o 14, molecular weight 583.84, spacer is P3 121, unit cell parameters is a=6.8765 (5), b=6.8765 (5), c=25.923 (4), Z=3, V=1061.56 (19) 3, Mohs' hardness is 2-3.
2. the preparation method of boronic acid compound lithium rubidium non-linear optic crystal according to claim 1, it is characterized in that adopting flux method growing crystal, concrete operation step is pressed and is carried out:
A, by compound L i 4rb 3b 7o 14in add fusing assistant Rb 2o, Rb 2cO 3, RbNO 3, Rb 2c 2o 4h 2o, RbOH or RbC 2h 3o 2, be heated to 700-1000 DEG C, then be cooled to 555-620 DEG C, obtain Li 4rb 3b 7o 14with the blend melt of fusing assistant;
B, with the speed slow cooling of 0.5-10 DEG C/h to room temperature, crystallization obtain seed crystal or use in cooling platinum filament suspension method obtain small-crystalline as seed crystal;
C, at compound L i 4rb 3b 7o 14with growing crystal in the blend melt of fusing assistant surface or blend melt: by the seed crystal that is fixed on seed rod from seed crystal crystal growing furnace top, make seed crystal and step a blend melt surface contact or stretch in blend melt, be cooled to 550-560 DEG C, then rotate seed crystal or crucible with the rotating speed of 0-100rpm;
D, to arrive after required yardstick until single crystal growing, make crystal depart from melt liquid level, be down to room temperature with the speed of temperature 1-100 DEG C/h, then slowly from burner hearth, take out crystal; Di lithium tetra borate rubidium nonlinear optic crystal can be obtained.
3. method according to claim 2, is characterized in that boronic acid compound lithium rubidium described in step a is Li containing the compound of lithium 2o, LiNO 3, LiOH, Li 2cO 3, LiC 2h 3o 2, Li 2c 2o 4h 2o, LiF or LiCl; Compound containing rubidium is Rb 2o, Rb 2cO 3, RbNO 3, Rb 2c 2o 4h 2o, RbOH, RbC 2h 3o 2, RbF or RbCl; Boron-containing compound is H 3bO 3or B 2o 3.
4. mixture according to claim 2, is characterized in that Li in step a 4rb 3b 7o 14be 1:0.1-3 with the mol ratio of solubility promoter.
5. a compound L i according to claim 1 4rb 3b 7o 14non-linear optic crystal is in the purposes of preparation times frequency generator, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
CN201310509439.2A 2013-10-24 2013-10-24 Compound lithium rubidium borate non-linear optical crystal as well as preparation method and application thereof Pending CN104562203A (en)

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Publication number Priority date Publication date Assignee Title
CN107217300A (en) * 2016-03-22 2017-09-29 中国科学院新疆理化技术研究所 Boronic acid compound sodium lithium and Boratex lithium optical crystal and preparation method and purposes
CN107217300B (en) * 2016-03-22 2019-07-09 中国科学院新疆理化技术研究所 Boronic acid compound sodium lithium and Boratex lithium optical crystal and preparation method and purposes
CN110468445A (en) * 2019-09-23 2019-11-19 中国科学院新疆理化技术研究所 Boric acid caesium barium nonlinear optical crystal and its preparation method and application
CN110468445B (en) * 2019-09-23 2021-03-09 中国科学院新疆理化技术研究所 Cesium barium borate nonlinear optical crystal and preparation method and application thereof
WO2021057151A1 (en) * 2019-09-23 2021-04-01 中国科学院新疆理化技术研究所 Cesium barium borate nonlinear optical crystal, preparation method therefor and use thereof

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Application publication date: 20150429