CN102212882A - Non-linear optical crystal of rubidium lithium borate compound, preparation method thereof and application thereof - Google Patents
Non-linear optical crystal of rubidium lithium borate compound, preparation method thereof and application thereof Download PDFInfo
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Abstract
The present invention relates to a kind of boronic acid compound lithium rubidium nonlinear optical crystal and its preparation method and application, which is Li5Rb2B7O14, belongs to rhombic system, space group Ama2, cell parameter are as follows:
Z=2,
Using compound melt method for crystal growth, obtain the large scale with Centimeter Level, the crystal is as the purposes for preparing device for non-linear optical times frequency generator, the nonlinear device times frequency generator made of di lithium tetra borate rubidium nonlinear optic crystal includes that will transmit through at least a branch of incident fundamental wave to generate the coherent light that at least a branch of frequency is different from incident light, the crystal has preparation speed fast, it is easy to operate, at low cost, the advantages that made crystalline size is big.
Description
Technical field
The present invention relates to a kind of compound lithium tetraborate rubidium non-linear optic crystal and its production and use, the chemical formula of this compound is Li
5Rb
2B
7O
14
Background technology
Utilize light wave frequency multiplication and mixing phenomenon, just can create the coherent light of needed various wavelength with present technical comparative maturity, some laser apparatus that output rating is very high again.For example, utilize frequency-doubling crystal that the laser of YAG laser apparatus output is done secondary frequency multiplication, obtain high-power green light; Make three times frequency multiplication, the acquisition wavelength is the purple light about 35.5 * 10-8 rice; Make four times frequency multiplication, obtaining wavelength is the UV-light of 26.5 * 10-8 rice.Equally, the optical wave-mixing phenomenon also is the good method that obtains the far infrared band coherent radiation.With carbon dioxide molecule laser apparatus output beam wavelength is the laser of 9.6 microns and 10.6 microns, in n type indium antimonide crystal, carry out photomixing, just can obtain the far infrared coherent light waves of wavelength about 100 microns, and in gallium arsenide semiconductor material, carry out optical wave-mixing by near the first-harmonic of several optical maser wavelengths of carbon dioxide molecule laser apparatus 10.6 microns, just can obtain light wave that wavelength and microwave region are joined.When making the light source of frequency multiplication and mixing with the dye laser of tunable wave length, also might let us obtain wavelength from vacuum ultraviolet (VUV) until far infrared, even the very high coherent light beam of power.
The nonlinear optical material main field of application is carried out the frequency inverted with frequency multiplication, frequency mixing technique except above-mentioned, also have that glory turns to, beam aberration elimination, zoom and conversion, optical information processing with optical signal control, light is limited and threshold values detects, optics connection entirely, optical computer, light storage and optical fiber communication and device etc.Lift a simple case again, non-linear optical crystal material is applied in the blue-green Laser, can be used to carry out separate (uranium isotope is a main raw material of making nuclear bomb) of uranium isotope (238U and 235U), can be in order to the initiated core fusion.In " Star War " of the U.S. in the works, the bluish-green laser device is one of basic weapon.Just because it has important strategic meaning like this, some high quick nonlinear optical material such as KTP (KTP) etc. have been listed in Department of State control military materials down, its outlet or produce the approval of all necessary process of mouth United States Government.Countries in the world are classified the research of nonlinear optical material high-tech as and are first developed project one after another at present, pay close attention.
The development of non-linear optic crystal removes the outstanding crystal of the performance of having found is improved growth technique, improves test, characterizes and estimate, and opens up outside the new application, and the development of exploring the non-linear optic crystal aspect that is applied to new wave band is noticeable.
Existing frequency inverted crystal is at ultraviolet, visible, near-infrared band, substantially needs have been satisfied, but at deep ultraviolet (particularly below the 200nm) and far infrared (particularly 5 μ m-20 μ m) two ends, non-linear optic crystal that can practicability still relatively lacks.Develop all solid state deep ultraviolet (200nm) coherent source, it is one of research project of present international optoelectronic areas forefront, this is because Ultra-Violet Laser has crucial application in many high-tech sectors, the ultraviolet coherent source all solid state as the IC etching Technology Need of a new generation; In photoelectron spectrum, the spectroscopic techniques, press for tunable all solid state deep ultraviolet coherent source, this will play critical effect for the development that promotes deep ultraviolet spectrum, energy spectrometer, and will open up a new material science research field.
Summary of the invention
The object of the invention is to provide a kind of compound lithium tetraborate rubidium non-linear optic crystal and its production and use, and the chemical formula of this compound is: Li
5Rb
2B
7O
14, this crystal belongs to rhombic system, and spacer is Ama2, and unit cell parameters is:
Z=2,
Another object of the present invention provides and adopts compound melting method, preparation compound lithium tetraborate rubidium non-linear optic crystal easy and simple to handle.
A further object of the present invention provides the purposes for preparing device for non-linear optical with compound lithium tetraborate rubidium non-linear optic crystal.
A further object of the present invention is to launch the blank spectral region of optical maser wavelengths in order to remedy all kinds of laser apparatus, thereby a kind of lithium tetraborate rubidium non-linear optic crystal is provided.
A kind of compound lithium tetraborate rubidium non-linear optic crystal of the present invention, this compound crystal molecular formula is Li
5Rb
2B
7O
14, this crystal belongs to rhombic system, and spacer is Ama2, and unit cell parameters is:
Z=2,
The preparation method of described compound lithium tetraborate rubidium non-linear optic crystal is to adopt compound melt method for growing crystal, and concrete operations follow these steps to carry out:
A, the lithium tetraborate rubidium compound is heated to fusing in crucible,, is cooled to 580-598 ℃ again, obtain Li at temperature 750-900 ℃ of constant temperature 1-100h
5Rb
2B
7O
14Melt;
B, slowly be cooled to room temperature with the speed of 0.5-10 ℃/h, spontaneous crystallization obtains seed crystal, or uses the platinum filament suspension method to obtain small-crystalline as seed crystal in cooling;
C, in compound bath surface or melt growing crystal: step b seed crystal is fixed on the seed rod, seed crystal contacts with step a bath surface under the top, be cooled to 590-580 ℃ with temperature 0-10 ℃/day speed, with the rotating speed rotary seed crystal rod of 0-100rpm or rotation crucible, with the speed of the 0-15mm/h pulling crystal that makes progress;
Or step a melt directly is cooled to 590-580 ℃, again be fixed on seed rod on seed crystal contact, with rotating speed rotary seed crystal rod or the rotation crucible of 0-100rpm, with the speed of the 0-15mm/h pulling crystal that makes progress;
D, treat that crystal growth stops after, strengthen pull rate, make crystal break away from melt liquid level, reduce to room temperature with the speed of 1-100 ℃/h, slowly from burner hearth, take out crystal then, can obtain compound lithium tetraborate rubidium non-linear optic crystal.
The compound that contains lithium in the described lithium tetraborate rubidium compound of step a is Li
2O, Li
2CO
3, LiNO
3, Li
2C
2O
4H
2O, LiOH, LiC
2H
3O
2, LiF or LiCl; The compound that contains 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
The described compound melt method for growing of step c crystal is that crystal pulling method or crucible move method.
Described compound lithium tetraborate rubidium non-linear optic crystal is as the purposes of preparation frequency multiplication producer.
Described frequency multiplication producer comprises a branch of at least incidence electromagnetic radiation and produces the device that a branch of at least frequency is different from the output radiation of incidence electromagnetic radiation after by at least one block of non-linear optic crystal.
Described lithium tetraborate rubidium compound is containing lithium, contain the compound of rubidium and boracic with equivalence ratio.
Compound lithium tetraborate rubidium non-linear optic crystal of the present invention, this crystal has following characteristics in preparation process:
Compound melt method for growing crystal is provided, in crucible, puts into and configure also pretreated raw material, this raw material fusing, growing crystal in bath surface or melt.And growing crystal can adopt crystal pulling method in the compound melt, and its method for preparing compound lithium tetraborate rubidium non-linear optic crystal comprises the steps:
At first the lithium tetraborate rubidium compound is heated to fusing in crucible,, is cooled to 580-598 ℃ again at temperature 750-900 ℃ of constant temperature 1-100h, stand-by; Slowly be cooled to room temperature spontaneous crystallization or use the platinum filament suspension method to obtain small-crystalline with the speed of 0.5-10 ℃/h, or existing crystal blank handled obtain seed crystal as seed crystal.
Adopting czochralski technique growing crystal in the compound melt: comprise and use seeded growth, during with seed crystal seed crystal is fixed on the seed rod that the compound bath surface for preparing in seed crystal and the crucible under the top contacts, and is cooled to 590-580 ℃; With the rotating speed of 0-100rpm rotation seed crystal and/or crucible, with the speed of the 15mm/h pulling crystal that makes progress; After treating that required yardstick is arrived in single crystal growing, strengthen pull rate, make crystal break away from melt liquid level, reduce to room temperature with the speed of 100 ℃/h, then with the Li for preparing
5Rb
2B
7O
14Non-linear optic crystal slowly takes out from burner hearth.
Or in the compound melt, adopt crucible to move the method growing crystal, with the speed mobile crucible of 0.01-10mm/h or well heater (the moving or vertical shifting of translation, can adopt seed crystal or without seed crystal), make melt solidify the generation monocrystalline by a temperature gradient zone; This process also can slowly be lowered the temperature by crystal growing furnace and be realized, type of heating can be resistance wire heating or globars or Si-Mo rod heating; The crucible shape can be a cylinder shape, and conical wedge angle is with in the bottom, boat type or other shape.
In principle, utilize existing compound melt growth technology can be used for preparing Li of the present invention
5Rb
2B
7O
14Crystal can obtain the Li of corresponding large-size when adopting the large size crucible
5Rb
2B
7O
14Crystal.
Preparation Li
5Rb
2B
7O
14The chemical equation of compound:
(1)LiNO
3+B
2O
3+Rb
2CO
3→Li
5Rb
2B
7O
14+NO
2↑+O
2↑;
(2)LiCH
3COO·nH
2O+B
2O
3+Rb
2CO
3+O
2→Li
5Rb
2B
7O
14+CO
2↑+H
2O↑;
(3)Li
2CO
3+B
2O
3+Rb
2CO
3→Li
5Rb
2B
7O
14+CO
2↑;
(4)LiOH+H
3BO
3+Rb
2O→Li
5Rb
2B
7O
14+H
2O↑;
(5)Li
2O+H
3BO
3+Rb
2O→Li
5Rb
2B
7O
14+H
2O↑;
(6)Li
2C
2O
4·nH
2O+H
3BO
3+Rb
2O+O
2→Li
5Rb
2B
7O
14+CO
2↑+H
2O↑;
(7)LiCl+B
2O
3+Rb
2O+O
2→Li
5Rb
2B
7O
14+Cl
2↑+H
2O↑。
Contain Li among the present invention, contain Rb and contain the B compound and can adopt commercially available reagent and raw material.
The compound lithium tetraborate rubidium non-linear optic crystal of the present invention's preparation is as the purposes of preparation device for non-linear optical frequency multiplication producer, and the described nonlinear device frequency multiplication producer of making of lithium tetraborate rubidium non-linear optic crystal comprises and will see through the coherent light that a branch of at least frequency of a branch of at least incident fundamental wave generation is different from incident light.Send light beam 2 by laser apparatus 1 and inject lithium tetraborate rubidium non-linear optic crystal 3, the outgoing beam 4 that is produced passes through filter plate 5, thereby obtains needed laser beam; This device for non-linear optical is a frequency multiplication producer etc.; Laser apparatus 1 is neodymium-doped yttrium-aluminum garnet (Nd:YAG) laser apparatus or other laser apparatus, does the frequency doubling device of light source using the Nd:YAG laser apparatus, and incoming beam 2 is that wavelength is the infrared light of 1064nm, passes through Li
5Rb
2B
7O
14It is the green frequency doubled light of 532nm that monocrystalline produces wavelength, and it is the infrared light of 1064nm and the green glow of 532nm that outgoing beam 4 contains wavelength, and the effect of filter plate 5 is elimination infrared light compositions, only allows green frequency doubled light to pass through.
The invention provides the device for non-linear optical that adopts the melt growth legal system to be equipped with compound lithium tetraborate rubidium non-linear optic crystal and to make with lithium tetraborate rubidium monocrystalline.Crystal system of the present invention is easily grown up and transparent no inclusion, have simple to operate, fast growth, cost is low, obtains advantages such as large-size crystal easily.
Description of drawings
Fig. 1 is a lithium tetraborate rubidium powder x-ray diffraction collection of illustrative plates of the present invention;
Fig. 2 is lithium tetraborate rubidium single crystal structure figure of the present invention;
Fig. 3 is the fundamental diagram of the device for non-linear optical of lithium tetraborate rubidium crystal making of the present invention, and wherein 1 is that laser apparatus, 2 is that light beam, 3 is that crystal, 4 is that outgoing beam, 5 is filter plate.
Embodiment
The present invention is described in detail below in conjunction with drawings and Examples:
Embodiment 1:
Synthetic compound Li
5Rb
2B
7O
14:
Adopt solid-state synthetic method to carry out sintering under 500 ℃ of high temperature, its chemical equation is: Li
2CO
3+ B
2O
3+ Rb
2CO
3→ Li
5Rb
2B
7O
14+ CO
2↑;
With Li
2CO
3, B
2O
3, Rb
2CO
3Put into mortar at 5: 7: 2 with stoichiometric ratio, mix and careful the grinding, in the opening corundum crucible of the Φ 100mm * 100mm that packs into then, it is compressed, put into retort furnace, slowly be warming up to 400 ℃, constant temperature 24 hours, take out crucible after cooling, this moment, sample was more loose, then took out sample and ground again evenly, place crucible again, in muffle furnace,,, put into mortar and smash grinding to pieces and promptly get Li its taking-up in 500 ℃ of constant temperature 48 hours again
5Rb
2B
7O
14Compound carries out X-ray analysis to this product, gained X-ray spectrogram and finished product Li
5Rb
2B
7O
14The monocrystalline last X-ray spectrogram of pulverizing is consistent;
In melt, adopt Czochralski grown lithium tetraborate rubidium (Li
5Rb
2B
7O
14) crystal:
At first with synthetic Li
5Rb
2B
7O
14Compound is packed in the opening platinum crucible of Φ 100mm * 100mm, crucible is put into crystal growing furnace be heated to fusing, is being warming up to 750 ℃, and constant temperature is cooled to 585 ℃ after 100 hours again, obtains Li
5Rb
2B
7O
14Melt;
Speed with 0.5 ℃/h of temperature slowly is cooled to room temperature, and spontaneous crystallization obtains seed crystal;
At compound bath surface growing crystal: the seed crystal that obtains is fixed on the seed rod, and seed crystal under the top imports crucible with the seed crystal that is fixed on the seed rod lower end from furnace roof portion aperture, makes seed crystal and Li
5Rb
2B
7O
140Melt liquid level contact directly is cooled to 580 ℃, and constant temperature is with the rotating speed rotary seed crystal rod of 50rpm, with the speed of the 15mm/h pulling crystal that makes progress;
After treating that crystal growth stops, strengthening pull rate, make crystal break away from melt liquid level, reduce to room temperature, slowly from burner hearth, take out crystal then, can obtain being of a size of the lithium tetraborate rubidium Li of 40mm * 40mm * 20mm with the speed of 80 ℃/h of temperature
5Rb
2B
7O
14Non-linear optic crystal.
Press embodiment 1 described method, reaction formula LiCl+B
2O
3+ Rb
2O+O
2→ Li
5Rb
2B
7O
14+ Cl
2↑+H
2O ↑ synthetic Li
5Rb
2B
7O
14Compound also can obtain Li
5Rb
2B
7O
14Crystal.
Embodiment 2:
Press reaction formula LiNO
3+ B
2O
3+ Rb
2CO
3→ Li
5Rb
2B
7O
14+ NO
2↑+O
2↑ synthetic compound Li
5Rb
2B
7O
14, the concrete operations step is carried out according to embodiment 1;
Adopt crystal pulling method to prepare Li
5Rb
2B
7O
14Crystal
With synthetic Li
5Rb
2B
7O
14Compound is put into the opening platinum crucible of Φ 70mm * 70mm, crucible is put into crystal growing furnace be heated to fusing, is being warming up to 1000 ℃, and constant temperature was cooled to 590 ℃ after 48 hours, obtained Li
5Rb
2B
7O
14Melt;
Speed with 10 ℃/h of temperature slowly is cooled to room temperature, uses the platinum filament suspension method to obtain small-crystalline as seed crystal in cooling;
At compound bath surface growing crystal: will be along the Li of c axle cutting
5Rb
2B
7O
14Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, and seed crystal is contacted with melt liquid level, directly is cooled to 581 ℃, and constant temperature is with the speed rotary seed crystal rod of 20rpm, with the speed of the 0.1mm/h pulling crystal that makes progress;
After treating that crystal growth stops, strengthening pull rate, make crystal break away from melt liquid level, reduce to room temperature, from burner hearth, take out crystal then lentamente, can obtain being of a size of the lithium tetraborate rubidium non-linear optic crystal of 40mm * 45mm * 15mm with the speed of 40 ℃/h of temperature.
Press embodiment 2 described methods, press reaction formula Li
2C
2O
4NH
2O+H
3BO
3+ Rb
2C
2O
4NH
2O+O
2→ Li
5Rb
2B
7O
14+ CO
2↑+H
2O ↑ synthetic Li
5Rb
2B
7O
14Compound also can obtain Li
5Rb
2B
7O
14Crystal.
Embodiment 3:
Press reaction formula LiOH+H
3BO
3+ Rb
2O → Li
5Rb
2B
7O
14+ H
2O ↑ synthetic Li
5Rb
2B
7O
14Compound, the concrete operations step is carried out according to embodiment 1;
Adopt crystal pulling method to prepare Li
5Rb
2B
7O
14Crystal
With synthetic Li
5Rb
2B
7O
14Compound is put into the opening platinum crucible of Φ 60mm * 60mm, crucible is put into crystal growing furnace be heated to fusing, is being warming up to 900 ℃, and constant temperature was cooled to 580 ℃ after 1 hour, obtained Li
5Rb
2B
7O
14Melt;
Speed with 1 ℃/h of temperature slowly is cooled to room temperature, and spontaneous crystallization obtains seed crystal;
At compound bath surface growing crystal: will be along the Li of c axle cutting
5Rb
2B
7O
14Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, and seed crystal is contacted with melt liquid level, is cooled to 583 ℃ with the speed of 0.5 ℃/day of temperature, with 100rpm speed rotary seed crystal rod, with the 5mm/h speed pulling crystal that makes progress;
After treating that crystal growth finishes, crystal is lifted from melt liquid level, reduce to room temperature, from burner hearth, take out crystal then lentamente, can obtain being of a size of the lithium tetraborate rubidium non-linear optic crystal of 45mm * 45mm * 45mm with the speed of 30 ℃/h of temperature.
Press embodiment 3 described methods, press reaction formula LiOH+H
3BO
3+ RbOH → Li
5Rb
2B
7O
14+ H
2O ↑ synthetic Li
5Rb
2B
7O
14Compound also can obtain Li
5Rb
2B
7O
14Crystal.
Embodiment 4:
Press reaction formula LiNO
3+ B
2O
3+ RbNO
3→ Li
5Rb
2B
7O
14+ NO
2↑+O
2↑ synthetic Li
5Rb
2B
7O
14Compound, the concrete operations step is carried out according to embodiment 1;
Adopt crystal pulling method to prepare Li
5Rb
2B
7O
14Crystal
With synthetic Li
5Rb
2B
7O
14Compound is put into the opening platinum crucible of Φ 100mm * 100mm, crucible is put into crystal growing furnace be heated to and dissolve, and is being warming up to 1000 ℃, and constant temperature was cooled to 590 ℃ after 24 hours, obtained Li
5Rb
2B
7O
14Melt;
Speed with 0.8 ℃/h of temperature slowly is cooled to room temperature, uses the platinum filament suspension method to obtain small-crystalline as seed crystal in cooling;
Growing crystal in the compound melt: will be along the Li of c axle cutting
5Rb
2B
7O
14Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, and seed crystal is immersed in the melt, directly is cooled to 585 ℃, constant temperature, and the seed rod speed of rotation is 0 (not rotating);
After treating that crystal growth finishes, crystal is lifted from melt liquid level, reduce to room temperature, from burner hearth, take out crystal then lentamente, can obtain being of a size of the lithium tetraborate rubidium non-linear optic crystal of 50mm * 45mm * 14mm with the speed of 1 ℃/h of temperature.
Press embodiment 4 described methods, press reaction formula LiOH+H
3BO
3+ RbNO
3→ Li
5Rb
2B
7O
14+ NO
2↑+O
2↑ synthetic Li
5Rb
2B
7O
14Compound also can obtain Li
5Rb
2B
7O
14Crystal.
Embodiment 5:
Press reaction formula LiCl+B
2O
3+ Rb
2CO
3→ Li
5Rb
2B
7O
14+ Cl
2↑+H
2O ↑ synthetic Li
5Rb
2B
7O
14Compound, the concrete operations step is carried out according to embodiment 1;
Adopt crucible to move legal system and be equipped with Li
5Rb
2B
7O
14Crystal
With synthetic Li
5Rb
2B
7O
14Compound is packed in the platinum crucible of Φ 10mm, the conical wedge angle of crucible bottom band, seed crystal is placed crucible bottom, crucible is put into the vertical process furnace, be warming up to after raw material melts fully, keep heating power constant, move down crucible, make melt solidify the generation crystal from bottom to top with the speed of 1mm/h;
Reduce to room temperature with the speed of 20 ℃/h of temperature after crystallization finishes, slowly from burner hearth, take out crucible, can obtain being of a size of the lithium tetraborate rubidium non-linear optic crystal of 15mm * 15mm * 10mm.
Press embodiment 5 described methods, press reaction formula LiCl+B
2O
3+ RbOH+O
2→ Li
5Rb
2B
7O
14+ Cl
2↑+H
2O ↑ synthetic Li
5Rb
2B
7O
14Compound also can obtain Li
5Rb
2B
7O
14Crystal.
Embodiment 6:
Press reaction formula Li
2C
2O
42H
2O+H
3BO
3+ Rb
2C
2O
4NH
2O+O
2→ Li
5Rb
2B
7O
14+ CO
2↑+H
2O ↑ synthetic Li
5Rb
2B
7O
14Compound, the concrete operations step is carried out according to embodiment 1;
Adopt crucible to move legal system and be equipped with Li
5Rb
2B
7O
14Crystal
With synthetic Li
5Rb
2B
7O
14Compound is packed into to be heated in the opening platinum crucible of Φ 80mm * 80mm and is dissolved, and is being warming up to 900 ℃, and constant temperature 80 hours is cooled to 595 ℃ again, obtains Li
5Rb
2B
7O
14Melt;
Speed with 5 ℃/h of temperature slowly is cooled to room temperature, uses the platinum filament suspension method to obtain small-crystalline as seed crystal in cooling;
Growing crystal in the compound melt: will be along the Li of c axle cutting
5Rb
2B
7O
14Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, and under the immersed in liquid level, with 10 ℃/day speed fast coolings to 582 ℃, with the speed rotation crucible of 80rpm, constant temperature is with the speed of the 15mm/h pulling crystal that makes progress;
After treating that crystal growth finishes, make crystal break away from liquid level, reduce to room temperature, slowly from burner hearth, take out crystal then, can obtain being of a size of the transparent lithium tetraborate rubidium non-linear optic crystal of 50mm * 70mm * 15mm with 60 ℃ of/hour speed of temperature.
Press embodiment 6 described methods, press reaction formula Li
2C
2O
42H
2O+H
3BO
3+ Rb
2CO
3→ Li
5Rb
2B
7O
14+ CO
2↑+H
2O ↑ synthetic Li
5Rb
2B
7O
14Compound also can obtain Li
5Rb
2B
7O
14Crystal.
Embodiment 7:
Press reaction formula Li
2CO
3+ B
2O
3+ Rb
2O → Li
5Rb
2B
7O
14+ CO
2↑ synthetic Li
5Rb
2B
7O
14Compound, the concrete operations step is carried out according to embodiment 1;
Adopt crystal pulling method to prepare Li
5Rb
2B
7O
14Crystal
With synthetic Li
5Rb
2B
7O
14Compound is packed into to be heated in the opening platinum crucible of Φ 100mm * 100mm and is dissolved, and is being warming up to 800 ℃, and constant temperature 10 hours is cooled to 593 ℃ again, obtains Li
5Rb
2B
7O
14Melt;
Speed with 7 ℃/h of temperature slowly is cooled to room temperature, and spontaneous crystallization obtains seed crystal;
At compound bath surface growing crystal: will be along the Li of c axle cutting
5Rb
2B
7O
14Brilliant be fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal imported crucible, make it to contact with liquid level, be cooled to 590 ℃ with the speed of 9 ℃/day of temperature, seed crystal does not rotate, with the speed of the 10mm/h pulling crystal that makes progress;
After treating that crystal growth finishes, make crystal break away from liquid level, reduce to room temperature, slowly from burner hearth, take out crystal then, can obtain being of a size of the transparent lithium tetraborate rubidium non-linear optic crystal of 35mm * 35mm * 10mm with 9 ℃/h of temperature speed.
Press embodiment 7 described methods, press reaction formula Li
2O+B
2O
3+ Rb
2O → Li
5Rb
2B
7O
14+ H
2O ↑ synthetic Li
5Rb
2B
7O
14Compound also can obtain Li
5Rb
2B
7O
14Monocrystalline.
Embodiment 8:
Press reaction formula LiOH+B
2O
3+ RbNO
3→ Li
5Rb
2B
7O
14+ NO
2↑+O
2↑ synthetic Li
5Rb
2B
7O
14Compound, the concrete operations step is carried out according to embodiment 1;
Adopt crystal pulling method to prepare Li
5Rb
2B
7O
14Crystal
With synthetic Li
5Rb
2B
7O
14Compound is packed into to be heated in the opening platinum crucible of Φ 150mm * 150mm and is dissolved, and is being warming up to 900 ℃, and constant temperature 60 hours is cooled to 598 ℃ again, obtains Li
5Rb
2B
7O
14Melt;
Speed with 3 ℃/h of temperature slowly is cooled to room temperature, uses the platinum filament suspension method to obtain small-crystalline as seed crystal in cooling;
At compound bath surface growing crystal: will be along the Li of c axle cutting
5Rb
2B
7O
14Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, makes it to contact with liquid level, with 9 ℃ of/day fast coolings to 578 of temperature ℃, constant temperature, with the rotating speed rotary seed crystal rod of 15rpm, with the speed of the 12mm/h pulling crystal that makes progress;
After treating that crystal growth finishes, make crystal break away from liquid level, reduce to room temperature, slowly from burner hearth, take out crystal then, can obtain being of a size of the transparent lithium tetraborate rubidium non-linear optic crystal of 50mm * 60mm * 15mm with 100 ℃/h speed.
Press embodiment 8 described methods, press reaction formula LiCH
3COOnH
2O+B
2O
3+ Rb
2CO
3+ O
2→ Li
5Rb
2B
7O
14+ CO
2↑+H
2O ↑ synthetic Li
5Rb
2B
7O
14Compound also can obtain Li
5Rb
2B
7O
14Crystal.
Embodiment 9:
Any one Li that embodiment 1-8 obtains
5Rb
2B
7O
14Crystal, frequency doubling device by the size 4mm * 4mm * 8mm of direction processing that is complementary, by being placed in shown in the accompanying drawing 3 on 3 the position, at room temperature, make light source with transferring Q Nd:YAG laser apparatus, incident wavelength is 1064nm, is that the infrared beam 2 of 1064nm is injected Li by transferring Q Nd:YAG laser apparatus 1 to send wavelength
5Rb
2B
7O
14Single crystal 3, producing wavelength is the green frequency doubled light of 532nm, and it is the infrared light of 1064nm and the green glow of 532nm that outgoing beam 4 contains wavelength, and filter plate 5 elimination infrared light compositions obtain the green laser that wavelength is 532nm.
Claims (5)
2. the preparation method of compound lithium tetraborate rubidium non-linear optic crystal according to claim 1 is characterized in that adopting compound melt method for growing crystal, and concrete operations follow these steps to carry out:
A, the lithium tetraborate rubidium compound is heated to fusing in crucible,, is cooled to 580-598 ℃ again, obtain Li at temperature 750-900 ℃ of constant temperature 1-100h
5Rb
2B
7O
14Melt;
B, slowly be cooled to room temperature with the speed of 0.5-10 ℃/h, spontaneous crystallization obtains seed crystal or uses the platinum filament suspension method to obtain small-crystalline as seed crystal in cooling;
C, in compound bath surface or melt growing crystal: step b seed crystal is fixed on the seed rod, seed crystal contacts with step a bath surface under the top, be cooled to 580-590 ℃ with temperature 0-10 ℃/day speed, with the rotating speed rotary seed crystal rod of 0-100rpm or rotation crucible, with the speed of the 0-15mm/h pulling crystal that makes progress;
Or step a melt directly is cooled to 580-590 ℃, again be fixed on seed rod on seed crystal contact, with rotating speed rotary seed crystal rod or the rotation crucible of 0-100rpm, with the speed of the 0-15mm/h pulling crystal that makes progress;
D, treat that crystal growth stops after, strengthen pull rate, make crystal break away from melt liquid level, reduce to room temperature with the speed of 1-100 ℃/h, slowly from burner hearth, take out crystal then, can obtain compound lithium tetraborate rubidium non-linear optic crystal.
3. method according to claim 2, the compound that it is characterized in that containing in the described lithium tetraborate rubidium compound of step a lithium is Li
2O, Li
2CO
3, LiNO
3, Li
2C
2O
4H
2O, LiOH, LiC
2H
3O
2, LiF or LiCl; The compound that contains 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. method according to claim 2 is characterized in that the described compound melt method for growing of step c crystal is that crystal pulling method or crucible move method.
5. compound lithium tetraborate rubidium non-linear optic crystal according to claim 1 is as the purposes of preparation frequency multiplication producer.
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