CN103628135B - Compound phospho-molybdic acid rubidium and phospho-molybdic acid rubidium non-linear optic crystal and preparation method and purposes - Google Patents

Compound phospho-molybdic acid rubidium and phospho-molybdic acid rubidium non-linear optic crystal and preparation method and purposes Download PDF

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CN103628135B
CN103628135B CN201210302050.6A CN201210302050A CN103628135B CN 103628135 B CN103628135 B CN 103628135B CN 201210302050 A CN201210302050 A CN 201210302050A CN 103628135 B CN103628135 B CN 103628135B
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molybdic acid
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CN103628135A (en
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潘世烈
王颖
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Abstract

The present invention relates to a kind of compound phospho-molybdic acid rubidium and phospho-molybdic acid rubidium non-linear optic crystal and preparation method and purposes, the chemical formula of this compound is Rb 4mo 5p 2o 22, adopt solid phase method preparation, the chemical formula of phospho-molybdic acid rubidium non-linear optic crystal is Rb 4mo 5p 2o 22, belong to rhombic system, spacer is C222 1, unit cell parameters is: z=4, its powder SHG effect is 1 times of KDP (KH 2pO 4), ultraviolet transmission region cut-off limit is 300nm, this crystal growing process has simple to operate, cost is low, and reagent used is inorganic raw material, and toxicity is low, growth cycle is short, the advantages such as physico-chemical property is stable, are suitable for making device for non-linear optical, can be used widely in the device for non-linear optical such as frequency-doubled conversion, optical parametric oscillator.

Description

Compound phospho-molybdic acid rubidium and phospho-molybdic acid rubidium non-linear optic crystal and preparation method and purposes
Technical field
The present invention relates to a kind of compound phospho-molybdic acid rubidium, chemical formula is Rb 4mo 5p 2o 22with the device for non-linear optical purposes that phospho-molybdic acid rubidium non-linear optic crystal and preparation method make with this crystal.
Background technology
Laser is widely used in the association areas such as scientific research, industry, traffic, national defence and health care as the coherent monochromatic source of a kind of high strength, good directionality.But the laser wavelength that current various laser apparatus directly export is limited, from ultraviolet band to infrared band, remain the blank wave band of laser.Due to the singularity of laser genesis mechanism, it can not be the laser medium that each wavelength searches out a kind of practicality.So utilize non-linear optic crystal to carry out frequency conversion has become Development of Laser Technology advanced subject with the various LASER Light Source obtaining broad tuning.
Non-linear optical effect originates from the interaction of laser and medium.When laser is when having the Propagation of non-zero second order susceptibility, the non-linear optical effect such as frequency multiplication and frequency, difference frequency, optically erasing can be produced.Non-linear optical crystal material has been deep into the every field of laser technology, has now become the requisite crystalline materials of technology such as the memory of laser frequency, Electro-optical Modulation and photorefractive crystal and storage.Nonlinear optical material main at present has: KDP (KH 2pO 4), BBO (β-BaB 2o 4), LBO (LiB 3o 5) etc., but due to a variety of causes, not yet obtain the various non-linear optic crystals that each wave band is all suitable for.
According to current inorganic nonlinear optical crystal Materials situation, novel inorganic non-linear optic crystal is not only required to have large Clock Multiplier Factor, but also require that its comprehensive performance parameter is good, be easy to generate high quality and large size body block crystal, this just needs to carry out a large amount of system and deep research work simultaneously.Explore the important topic that high performance novel nonlinear optical crystal material is photoelectric functional material field, people are still constantly exploring in the hope of finding the better non-linear optic crystal of performance.
Summary of the invention
The object of the invention is to be applied to the needs of the nonlinear optical material of all-solid state laser system for solving, and provide a kind of compound phospho-molybdic acid rubidium and phospho-molybdic acid rubidium non-linear optic crystal and preparation method and purposes, the chemical formula of this compound is Rb 4mo 5p 2o 22, adopt solid reaction process, after mixing containing rubidium, leaded, boracic and phosphorous raw material, solid state reaction is carried out in heating, obtains the compound of phospho-molybdic acid rubidium, then this compound is adopted melt method for crystal growth, can obtain phospho-molybdic acid rubidium non-linear optic crystal.This compound is the non-linear optic crystal with the large-sized rhombic system of centimetre-sized, and spacer is C222 1, unit cell parameters is: z=4, its powder SHG effect is 1 times of KDP (KH 2pO 4), ultraviolet transmission region cut-off limit is 300nm, is suitable for making device for non-linear optical.
A kind of compound phospho-molybdic acid rubidium of the present invention, the chemical formula of this compound is Rb 4mo 5p 2o 22, molecular weight is 1235.52, adopts solid reaction process preparation.
A kind of compound phospho-molybdic acid rubidium non-linear optic crystal, the chemical formula of this crystal is Rb 4mo 5p 2o 22, molecular weight is 1235.52, belongs to rhombic system, and spacer is C222 1, unit cell parameters is z=4,
Described compound phospho-molybdic acid rubidium and the preparation method of non-linear optic crystal thereof, adopt solid reaction process and compound melt method for crystal growth, concrete operations follow these steps to carry out:
A, will containing rubidium compound, molybdate compound and P contained compound take put into mortar in molar ratio at 4: 5: 2, mixing is also carefully ground, load corundum crucible, put into retort furnace, slowly be warming up to 400 DEG C, constant temperature 12 hours, gas is drained only as far as possible, take out crucible after cooling, by sample grinding evenly, be placed in crucible again, retort furnace is warming up to 500 DEG C, sample took out after 48 hours by constant temperature, put into mortar to smash grinding to pieces and namely obtain phospho-molybdic acid rubidium compound single-phase polycrystalline powder, again X-ray analysis is carried out to this polycrystal powder, gained X-ray spectrogram and finished product Rb 4mo 5p 2o 22monocrystalline last X-ray spectrogram of pulverizing is consistent,
B, phospho-molybdic acid rubidium compound is heated to fusing in crucible, at temperature 650-700 DEG C of constant temperature 4-15h, then is cooled to 530 DEG C-540 DEG C, obtains phospho-molybdic acid rubidium compound melt;
C, with the speed slow cooling of temperature 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;
D, in compound bath surface or melt growing crystal: the seed crystal obtained by step c is fixed on seed rod, seed crystal from crystal growing furnace top, seed crystal and phospho-molybdic acid rubidium compound bath surface is made to contact or stretch in phospho-molybdic acid rubidium compound melt, be cooled to 510-520 DEG C, constant temperature or lower the temperature with the speed of temperature 0.1-10 DEG C/day, with the rotating speed rotary seed crystal rod of 0-100rpm, with the speed of 0-15mm/h upwards lifting crystal growth;
Or step b compound melt is directly cooled to 510-520 DEG C, contact with the seed crystal be fixed on seed rod again, constant temperature or with the speed of temperature 0.1-10 DEG C of/day cooling, with the rotating speed rotary seed crystal rod of 0-100rpm, with the speed of 0-15mm/h upwards lifting crystal growth;
E, arrive after required yardstick until crystal growth, by crystal lift-off bath surface, be down to room temperature with the speed of temperature 1-100 DEG C/h, phospho-molybdic acid rubidium non-linear optic crystal can be obtained.
Compound containing rubidium described in step a is Rb 2o, Rb 2cO 3, RbNO 3, Rb 2c 2o 4h 2o, RbOH, RbC 2h 3o 2, RbHCO 3or RbF; Compound containing molybdenum is MoO 3, H 2moO 4h 2o, (NH 4) 2moO 4or (NH 4) 2mo 2o 7; Phosphorous compound is NH 4h 2pO 4, (NH 4) 2hPO 4or P 2o 5.
Preparing crystal in steps d adopts kyropoulos, crystal pulling method or falling crucible method to prepare Rb 4mo 5p 2o 22crystal.
The purposes of described phospho-molybdic acid rubidium non-linear optic crystal, this crystal be used for preparation times frequency generator, on or lower frequency transmodulator or optical parametric oscillator.
At least a branch of incidence electromagnetic radiation to be 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 is comprised as preparation times frequency generator, upper or lower frequency transmodulator or optical parametric oscillator.
Compound phospho-molybdic acid rubidium of the present invention and phospho-molybdic acid rubidium non-linear optic crystal and preparation method and purposes, in principle, adopt general chemical synthesis process can prepare compound R b 4mo 5p 2o 22, existing preferred solid reaction process, that is: by containing rubidium, containing molybdenum and phosphorous raw material in molar ratio 4: 5: 2 weigh and mix after, solid state reaction is carried out in heating, and can obtain chemical expression is Rb 4mo 5p 2o 22compound, chemical equation is:
(1)2Rb 2CO 3+5MoO 3+2NH 4H 2PO 4＝Rb 4Mo 5P 2O 22+3H 2O↑+2CO 2↑+2NH 3↑
(2)2Rb 2O+5MoO 3+2NH 4H 2PO 4＝Rb 4Mo 5P 2O 22+2NH 3↑+3H 2O↑
(3)2Rb 2O+5MoO 3+P 2O 5＝Rb 4Mo 5P 2O 22
(4)2Rb 2CO 3+5MoO 3+P 2O 5＝Rb 4Mo 5P 2O 22+2CO 2↑
(5)4RbOH+5MoO 3+2NH 4H 2PO 4＝Rb 4Mo 5P 2O 22+2NH 3↑+5H 2O↑
(6)4RbNO 3+5MoO 3+P 2O 5＝Rb 4Mo 5P 2O 22+4NO 2↑+O 2↑
(7)4RbNO 3+5H 2MoO 4·H 2O+P 2O 5＝Rb 4Mo 5P 2O 22+4NO 2↑+O 2↑+10H 2O↑
(8)4Rb 2CO 3+5(NH 4) 2Mo 2O 7+4(NH 4) 2HPO 4＝2Rb 4Mo 5P 2O 22+4CO 2↑+18NH 3↑+11H 2O↑
(9)2Rb 2CO 3+5(NH 4) 2MoO 4+2NH 4H 2PO 4＝Rb 4Mo 5P 2O 22+2CO 2↑+12NH 3↑+8H 2O↑
(10)2Rb 2C 2O 4·H 2O+5(NH 4) 2MoO 4+2NH 4H 2PO 4＝Rb 4Mo 5P 2O 22+2CO 2↑+2CO↑+12NH 3↑+10H 2O↑
Compound phospho-molybdic acid rubidium of the present invention and phospho-molybdic acid rubidium non-linear optic crystal and preparation method and purposes, wherein compound phospho-molybdic acid rubidium is congruent compound, the crystal of this compound, it is the non-linear optic crystal of rhombic system, and spacer is C222 1, unit cell parameters is: z=4, its powder SHG effect is 1 times of KDP (KH 2pO 4).At growth Rb 4mo 5p 2o 22during monocrystalline, can not cause having foreign ion to enter lattice, product purity is high, fast growth, cost is low, obtain crystal there is larger degree of birefringence, hardness is comparatively large, good mechanical property, be easy to cutting, polishing and preservation, the advantage such as not easily broken, is suitable for making device for non-linear optical.
The invention provides the preparation method of compound phospho-molybdic acid rubidium non-linear optic crystal, adopt compound melt method for crystal growth, the Rb being of a size of centimetre-sized can be obtained 4mo 5p 2o 22single crystal; Use large size crucible, then can obtain the single crystal of corresponding large-size, this crystal birefringence rate is large, expands the research field of nonlinear crystalline material.
Accompanying drawing explanation
Fig. 1 is the X-ray powder diffraction pattern of phospho-molybdic acid rubidium crystal of the present invention.
Fig. 2 is phospho-molybdic acid rubidium single crystal structure figure of the present invention.
Fig. 3 is the fundamental diagram of the device for non-linear optical that the present invention makes, be laser apparatus comprising (1), (2) be convex lens, (3) be phospho-molybdic acid rubidium non-linear optic crystal, (4) be beam splitting prism, (5) be filter plate, ω is 2 times that the frequency of refracted light equals incident light frequency or incident light frequency.
Embodiment
Embodiment 1:
By chemical formula: 2Rb 2cO 3+ 5MoO 3+ 2NH 4h 2pO 4=Rb 4mo 5p 2o 22+ 3H 2o ↑+2CO 2↑+2NH 3↑, adopt solid reaction process synthesis phospho-molybdic acid rubidium (Rb 4mo 5p 2o 22) compound:
Take raw material according to reaction formula ratio and put into mortar, mixing is also carefully ground, and puts it in the opening corundum crucible of Φ 400mm × 400mm, compress, put into retort furnace, be slowly warming up to 400 DEG C, constant temperature 24 hours, take out crucible after cooling, now sample is more loose, then takes out sample and again grinds evenly, be placed in crucible again, in temperature 500 DEG C of constant temperature 48 hours in retort furnace, taken out, put into mortar and smash grinding to pieces and namely obtain Rb 4mo 5p 2o 22compound, carries out X-ray analysis to this product, gained X-ray spectrogram and Rb 4mo 5p 2o 22monocrystalline last X-ray spectrogram of pulverizing is consistent;
Crystal pulling method is adopted to prepare Rb in the melt 4mo 5p 2o 22crystal:
By the Rb of synthesis 4mo 5p 2o 22compound loads in the opening platinum crucible of Φ 100mm × 100mm, then crucible is put into crystal growing furnace, and be warming up to 700 DEG C, constant temperature, after 15 hours, is cooled to 530 DEG C, obtains phospho-molybdic acid rubidium compound melt;
With the speed slow cooling of temperature 0.5 DEG C/h to room temperature, crystallization obtains seed crystal;
The Rb of seed rod lower end will be fixed on 4mo 5p 2o 22seed crystal imports crucible from furnace roof portion aperture, seed crystal is contacted with phospho-molybdic acid rubidium compound melt liquid level, is cooled to 510 DEG C, with the cooling of the speed of temperature 1 DEG C of/day, with 50rpm rotating speed rotary seed crystal rod, with the speed of 15mm/h upwards lifting crystal growth;
Strengthen pull rate when terminating growth, arrive after required yardstick until crystal growth, make crystal depart from 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 Rb being of a size of 36mm × 34mm × 30mm 4mo 5p 2o 22crystal.
By method described in embodiment 1, reaction formula 4RbNO 3+ 5MoO 3+ P 2o 5=Rb 4mo 5p 2o 22+ 4NO 2↑+O 2↑ synthesis Rb 4mo 5p 2o 22compound, also can obtain Rb 4mo 5p 2o 22crystal.
Embodiment 2:
By reaction formula 2Rb 2o+5MoO 3+ P 2o 5=Rb 4mo 5p 2o 22synthesis Rb 4mo 5p 2o 22compound, concrete operation step carries out according to embodiment 1;
Crystal pulling method is adopted to prepare Rb 4mo 5p 2o 22crystal
By the Rb of synthesis 4mo 5p 2o 22compound puts into the opening platinum crucible of Φ 90mm × 90mm, then crucible is put into crystal growing furnace, is warming up to 650 DEG C, and constant temperature, after 10 hours, is cooled to 540 DEG C, obtains phospho-molybdic acid rubidium compound melt;
With the speed slow cooling of temperature 0.5 DEG C/h to room temperature, crystallization obtains seed crystal;
By Rb 4mo 5p 2o 22seed crystal platinum filament is fixed on seed rod lower end, from furnace roof portion aperture, seed crystal is imported crucible, and seed crystal is contacted with phospho-molybdic acid rubidium compound melt liquid level, be cooled to 510 DEG C, with the cooling of the speed of temperature 1 DEG C of/day, with 20rpm rotating speed rotary seed crystal rod, with the speed of 0.1mm/h upwards lifting crystal growth;
Strengthen pull rate when terminating growth, arrive after required yardstick until crystal growth, 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 Rb being of a size of 60mm × 40mm × 25mm 4mo 5p 2o 22monocrystalline.
By method described in embodiment 2, reaction formula 2Rb 2o+5MoO 3+ 2NH 4h 2pO 4=Rb 4mo 5p 2o 22+ 2NH 3↑+3H 2o ↑ synthesis Rb 4mo 5p 2o 22compound, also can obtain Rb 4mo 5p 2o 22crystal.
Embodiment 3:
By reaction formula 2Rb 2cO 3+ 5 (NH 4) 2moO 4+ 2NH 4h 2pO 4=Rb 4mo 5p 2o 22+ 2CO 2↑+12NH 3↑+8H 2o ↑ synthesis Rb 4mo 5p 2o 22compound, concrete operation step carries out according to embodiment 1;
Kyropoulos is adopted to prepare Rb 4mo 5p 2o 22crystal
By the Rb of synthesis 4mo 5p 2o 22compound puts into the opening platinum crucible of Φ 80mm × 80mm, then crucible is put into crystal growing furnace, is warming up to 650 DEG C, and constant temperature, after 4 hours, is cooled to 520 DEG C, obtains phospho-molybdic acid rubidium compound melt;
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;
By Rb 4mo 5p 2o 22seed crystal platinum filament is fixed on seed rod lower end, from furnace roof portion aperture, seed crystal is imported crucible, and seed crystal is contacted with phospho-molybdic acid rubidium compound melt liquid level, be cooled to 515 DEG C, with the cooling of the speed of temperature 10 DEG C of/day, with the rotating speed rotary seed crystal rod of 100rpm, not upwards lifting crystal growth;
Arrive after required yardstick until crystal growth, 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 Rb being of a size of Φ 20mm × 20mm × 35mm 4mo 5p 2o 22crystal.
By method described in embodiment 3, reaction formula 4Rb 2cO 3+ 5 (NH 4) 2mo 2o 7+ 4 (NH 4) 2hPO 4=2Rb 4mo 5p 2o 22+ 4CO 2↑+18NH 3↑+11H 2o ↑ synthesis Rb 4mo 5p 2o 22compound, also can obtain Rb 4mo 5p 2o 22crystal.
Embodiment 4:
By reaction formula 2Rb 2c 2o 4h 2o+5 (NH 4) 2moO 4+ 2NH 4h 2pO 4=Rb 4mo 5p 2o 22+ 2CO 2↑+2CO ↑+12NH 3↑+10H 2o ↑ synthesis Rb 4mo 5p 2o 22compound, concrete operation step carries out according to embodiment 1;
Kyropoulos is adopted to prepare Rb 4mo 5p 2o 22crystal
By the Rb of synthesis 4mo 5p 2o 22compound puts into the opening platinum crucible of Φ 100mm × 100mm, then crucible is put into crystal growing furnace, is warming up to 680 DEG C, and constant temperature, after 10 hours, is cooled to 530 DEG C, obtains phospho-molybdic acid rubidium compound melt;
By Rb 4mo 5p 2o 22seed 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 510 DEG C, constant temperature, non rotating seed rod, with the speed of 15mm/h upwards lifting crystal growth;
Strengthen pull rate when terminating growth, arrive after required yardstick until crystal growth, by crystal lift-off melt liquid level, be down to room temperature with the speed of temperature 1 DEG C/h, then from burner hearth, take out crystal lentamente, obtain the Rb being of a size of Φ 50mm × 42mm × 14mm 4mo 5p 2o 22crystal.
Embodiment 5:
By reaction formula 4RbNO 3+ 5MoO 3+ P 2o 5=Rb 4mo 5p 2o 22+ 4NO 2↑+O 2↑ synthesis Rb 4mo 5p 2o 22compound, concrete operation step carries out according to embodiment 1;
Kyropoulos is adopted to prepare Rb 4mo 5p 2o 22crystal
By the Rb of synthesis 4mo 5p 2o 22compound puts into the opening platinum crucible of Φ 80mm × 80mm, then crucible is put into crystal growing furnace, is warming up to 680 DEG C, and constant temperature, after 10 hours, obtains Rb 4mo 5p 2o 22melt;
Melt is directly cooled to 510 DEG C, by Rb 4mo 5p 2o 22seed 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, with the speed of 0.1 DEG C of/day cooling, and non rotating seed rod, not upwards pulling crystal;
Arrive after required yardstick until crystal growth, by crystal lift-off melt liquid level, be down to room temperature with the speed of temperature 5 DEG C/h, then from burner hearth, take out crystal lentamente, obtain the Rb being of a size of Φ 20mm × 18mm × 14m 4mo 5p 2o 22crystal.
Embodiment 6:
Reaction formula 2Rb 2cO 3+ 5MoO 3+ 2NH 4h 2pO 4=Rb 4mo 5p 2o 22+ 3H 2o ↑+2CO 2↑+2NH 3↑ synthesis Rb 4mo 5p 2o 22compound, concrete operation step carries out according to embodiment 1;
Falling crucible method is adopted to prepare Rb 4mo 5p 2o 22crystal:
By the Rb of synthesis 4mo 5p 2o 22compound loads in the platinum crucible of Φ 10mm, the conical wedge angle of crucible bottom band, seed crystal is placed in crucible bottom, crucible is put into vertical process furnace, be warming up to after raw material melts completely, keep heating power constant, with the speed decline crucible of 1mm/h, make melt solidify generation monocrystalline from bottom to top, after crystallization, be down to room temperature with the speed of temperature 20 DEG C/h, slowly from burner hearth, take out crucible, obtain the Rb being of a size of Φ 10mm × 25mm 4mo 5p 2o 22monocrystalline.
Described in embodiment 6, reaction formula 4RbNO 3+ 5MoO 3+ P 2o 5=Rb 4mo 5p 2o 22+ 4NO 2↑+O 2↑ synthesis Rb 4mo 5p 2o 22compound, also can obtain Rb 4mo 5p 2o 22crystal.
Embodiment 7:
By the Rb of gained in embodiment 1-6 4mo 5p 2o 22crystal, is placed on the position of 3 by shown in accompanying drawing 3, and at room temperature, export with adjusting the 1064nm of QNd:YAG laser apparatus and make light source, observe obvious 532nm frequency doubling green light and export, output intensity is about 2 times of equal conditions KDP; Figure 3 shows that, sending wavelength by adjusting QNd:YAG laser apparatus 1 is that the infrared beam of 1064nm injects phospho-molybdic acid rubidium non-linear optic crystal through convex lens 2, 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, after filter plate 5 elimination, obtain the frequency doubled light that wavelength is 532nm.

Claims (4)

1. a compound phospho-molybdic acid rubidium non-linear optic crystal, is characterized in that the chemical formula of this crystal is Rb 4mo 5p 2o 22, molecular weight is 1235.52, belongs to rhombic system, and spacer is C222 1, unit cell parameters is z=4,
2. the preparation method of compound phospho-molybdic acid rubidium non-linear optic crystal according to claim 1, it is characterized in that adopting solid reaction process and compound melt method for crystal growth, concrete operations follow these steps to carry out:
A, will be Rb containing rubidium compound 2o, Rb 2cO 3, RbNO 3, Rb 2c 2o 4h 2o, RbOH, RbC 2h 3o 2, RbHCO 3or RbF, molybdate compound is MoO 3, H 2moO 4h 2o, (NH 4) 2moO 4or (NH 4) 2mo 2o 7be NH with P contained compound 4h 2pO 4, (NH 4) 2hPO 4or P 2o 5take put into mortar at 4: 5: 2 in molar ratio, mixing is also carefully ground, load corundum crucible, put into retort furnace, slowly be warming up to 400 DEG C, constant temperature 12 hours, gas is drained only as far as possible, take out crucible after cooling, by sample grinding evenly, be placed in crucible again, retort furnace is warming up to 500 DEG C, sample took out after 48 hours by constant temperature, put into mortar and smashed grinding to pieces and namely obtain phospho-molybdic acid rubidium compound single-phase polycrystalline powder, again X-ray analysis is carried out to this polycrystal powder, gained X-ray spectrogram and finished product Rb 4mo 5p 2o 22monocrystalline last X-ray spectrogram of pulverizing is consistent;
B, phospho-molybdic acid rubidium compound is heated to fusing in crucible, at temperature 650-700 DEG C of constant temperature 4-15h, then is cooled to 530 DEG C-540 DEG C, obtains phospho-molybdic acid rubidium compound melt;
C, with the speed slow cooling of temperature 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;
D, in compound bath surface or melt growing crystal: the seed crystal obtained by step c is fixed on seed rod, seed crystal from crystal growing furnace top, seed crystal and phospho-molybdic acid rubidium compound bath surface is made to contact or stretch in phospho-molybdic acid rubidium compound melt, be cooled to 510-520 DEG C, constant temperature or lower the temperature with the speed of temperature 0.1-10 DEG C/day, with the rotating speed rotary seed crystal rod of 0-100rpm, with the speed of 0.1-15mm/h upwards lifting crystal growth;
Or step b compound melt is directly cooled to 510-520 DEG C, contact with the seed crystal be fixed on seed rod again, constant temperature or with the speed of temperature 0.1-10 DEG C of/day cooling, with the rotating speed rotary seed crystal rod of 0.1-100rpm, with the speed of 0-15mm/h upwards lifting crystal growth;
E, arrive after required yardstick until crystal growth, by crystal lift-off bath surface, be down to room temperature with the speed of temperature 1-100 DEG C/h, phospho-molybdic acid rubidium non-linear optic crystal can be obtained.
3. method according to claim 2, is characterized in that preparing crystal in steps d adopts kyropoulos or falling crucible method to prepare Rb 4mo 5p 2o 22crystal.
4. the purposes of phospho-molybdic acid rubidium non-linear optic crystal according to claim 1, is characterized in that this crystal is for the preparation of doubly frequency generator, upper or lower frequency transmodulator or optical parametric oscillator.
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