CN103590107B - Boronic acid compound caesium zinc and boric acid caesium zinc non-linear optic crystal and Preparation method and use - Google Patents

Boronic acid compound caesium zinc and boric acid caesium zinc non-linear optic crystal and Preparation method and use Download PDF

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CN103590107B
CN103590107B CN201210293692.4A CN201210293692A CN103590107B CN 103590107 B CN103590107 B CN 103590107B CN 201210293692 A CN201210293692 A CN 201210293692A CN 103590107 B CN103590107 B CN 103590107B
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CN103590107A (en
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潘世烈
俞洪伟
吴红萍
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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 boronic acid compound caesium zinc and boric acid caesium zinc non-linear optic crystal and Preparation method and use, the chemical formula of this boronic acid compound caesium zinc is Cs 3zn 6b 9o 21, molecular weight 1224.24, the chemical formula of boronic acid compound caesium zinc non-linear optic crystal is Cs 3zn 6b 9o 21, molecular weight 1224.24, belongs to rhombic system, spacer Cmc2 1, unit cell parameters is , its powder SHG effect reaches KDP (KH 2pO 4) 3 times, boronic acid compound caesium zinc adopt solid reaction process synthesis; Boric acid caesium zinc non-linear optic crystal adopts the growth of high temperature solution method, this boric acid caesium zinc non-linear optic crystal mechanical hardness is large, be easy to cutting, polishing and preservation, be used widely in the device for non-linear optical such as preparation times frequency generator, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.

Description

Boronic acid compound caesium zinc and boric acid caesium zinc non-linear optic crystal and Preparation method and use
Technical field
The present invention relates to chemical formula is Cs 3zn 6b 9o 21boronic acid compound caesium zinc and boric acid caesium zinc non-linear optic crystal, the preparation method of crystal and the device for non-linear optical utilizing this crystal to make.
Background technology
Non-linear optical crystal material is one of important photoelectric information functional material, be the important substance basis of photoelectron technology particularly laser technology, be with a wide range of applications and huge using value in information, the energy, field such as industry manufacture, medical science, scientific research, military affairs etc.The research of novel nonlinear optical crystal material is all placed on the position of first developing by each developed country of the world, and lists in the research project of every country as a grand strategy measure.
Borate crystal due to its band gap comparatively large, two-photon absorption probability is little, and laser damage threshold is higher, is beneficial to the non-linear optical effect that acquisition is stronger, is the ideal chose of new ultra-violet non-linear optic crystal.And d 0, d 10deng transition-metal cation be incorporated in borate and can increase frequency-doubled effect further.Therefore, the boratory synthesis of transition metal will be the effective means designing large frequency-doubled effect ultraviolet nonlinear optical material.
Summary of the invention
The object of the invention is to provide a kind of boronic acid compound caesium zinc, and boric acid caesium zinc non-linear optic crystal, and chemical formula is Cs 3zn 6b 9o 21.
Another object of the present invention is to provide the preparation method adopting solid reaction process synthetic compound and high temperature solution method growth boric acid caesium zinc non-linear optic crystal.
Further object of the present invention is to provide a kind of purposes of boric acid caesium zinc device for non-linear optical, for the preparation of doubly frequency generator, upper or lower frequency transmodulator or optical parametric oscillator.
A kind of boronic acid compound caesium zinc of the present invention, the chemical formula of this compound is Cs 3zn 6b 9o 21, molecular weight 1224.24, adopts solid reaction process synthetic compound.
A kind of boronic acid compound caesium zinc non-linear optic crystal, this crystal-chemical formula is Cs 3zn 6b 9o 21, molecular weight 1224.24, does not have symmetry centre, belongs to rhombic system, spacer Cmc2 1, unit cell parameters is z=4, its powder SHG effect reaches KDP (KH 2pO 4) 3 times.
The preparation method of described boric acid caesium zinc non-linear optic crystal, adopt solid reaction process synthetic compound and high temperature solution method growth boric acid caesium zinc non-linear optic crystal, concrete operations follow these steps to carry out:
A, by boric acid caesium zn cpds single-phase polycrystalline powder and fusing assistant Homogeneous phase mixing, temperature 650-1000 DEG C is heated to the temperature rise rate of temperature 1-30 DEG C/h, constant temperature 5-80 hour, obtain mixed molten liquid, be cooled to temperature 500-800 DEG C again, the mol ratio of its mesoboric acid caesium zn cpds single-phase polycrystalline powder and fusing assistant is 1: 1-6;
Or directly will mix with fusing assistant containing Cesium compound, zinc compound and boric acid, temperature 650-1000 DEG C is heated to the temperature rise rate of temperature 1-30 DEG C/h, constant temperature 5-80 hour, obtain mixed molten liquid, be cooled to temperature 500-800 DEG C again, the mol ratio wherein containing Cesium compound, zinc compound and boric acid and fusing assistant is 1-2: 2-4: 3-6: 1-18;
B, prepare boric acid caesium zinc seed crystal: the mixed molten liquid obtained by step a is slowly down to room temperature with the speed of temperature 3-10 DEG C/h, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
C, the crucible filling the mixed molten liquid that step a obtains is inserted in crystal growing furnace, the seed crystal obtained by step b is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 5-60 minute, seed crystal is carried out melt back in contact mixed molten liquid liquid level or mixed molten liquid, constant temperature 5-60 minute, is down to temperature of saturation with the speed of temperature 1-60 DEG C/h;
D, again with the speed slow cooling of temperature 0.1-5 DEG C/day, the growth of crystal is carried out with 0-60rpm rotating speed rotary seed crystal rod, arrive after required yardstick until single crystal growing, by crystal lift-off mixed molten liquid surface, and be down to room temperature with temperature 1-80 DEG C/h speed, then crystal is taken out from burner hearth, boric acid caesium zinc non-linear optic crystal can be obtained.
Containing Cesium compound in boric acid caesium zinc described in step a is Cs 2o, CsF, CsCl, Cs 2cO 3, CsNO 3, CsOH, Cs 2c 2o 4h 2o or Cs 2c 2h 3o 2, zinc compound is ZnO, Zn (NO 3) 2, ZnCO 3, ZnC 2h 3o 2, Zn (OH) 2or ZnCl 2boron-containing compound is H 3bO 3or B 2o 3.
Fusing assistant described in step a is Cs 2o-B 2o 3, Cs 2o-PbO, CsF-B 2o 3, CsF-PbO, B 2o 3-PbO or B 2o 3-PbO-Cs 2o.
Fusing assistant Cs 2o-B 2o 3cs in system 2o and B 2o 3mol ratio be 1-3: 2-5; Cs 2cs in O-PbO system 2o and PbO mol ratio is 1-3: 3-8; CsF-B 2o 3csF and B in system 2o 3mol ratio be 1-6: 2-5; In CsF-PbO system, CsF and PbO mol ratio is 1-6: 3-8; B 2o 3b in-PbO system 2o 3be 2-5: 3-8 with PbO mol ratio; B 2o 3-PbO-Cs 2b in O system 2o 3, Cs 2o and PbO mol ratio is 2-5: 1-6: 3-8.
The purposes of described boric acid caesium zinc non-linear optic crystal, this boric acid caesium zinc non-linear optic crystal is for the preparation of doubly frequency generator, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
Boric acid caesium zn cpds provided by the invention, its chemical formula is Cs 3zn 6b 9o 21, it adopts solid reaction process to prepare boric acid caesium zn cpds by following chemical equation:
(1)3Cs 2CO 3+12ZnO+18H 3BO 3→2Cs 3Zn 6B 9O 21+3CO 2↑+27H 2O↑
(2)6CsNO 3+12ZnO+18H 3BO 3→2Cs 3Zn 6B 9O 21+6NO 2↑+27H 2O↑+3O 2↑
(3)6CsHCO 3+12ZnO+18H 3BO 3→2Cs 3Zn 6B 9O 21+6CO 2↑+27H 2O↑
(4)3Cs 2CO 3+12ZnO+9B 2O 3→2Cs 3Zn 6B 9O 21+3CO 2↑
(5)6CsNO 3+12ZnO+9B 2O 3→2Cs 3Zn 6B 9O 21+6NO 2↑+3O 2↑
(6)6CsHCO 3+12ZnO+9B 2O 3→2Cs 3Zn 6B 9O 21+6CO 2↑+3H 2O↑
(7)3Cs 2C 2O 4+12ZnO+9B 2O 3→2Cs 3Zn 6B 9O 21+2CO 2↑+4CO↑
(8)6CsCl+12ZnO+9B 2O 3→2Cs 3Zn 6B 9O 21+3Cl 2↑
Obtain crystal there is wider transmission region, hardness is comparatively large, good mechanical property, and not easily broken and deliquescence is easy to the advantages such as processing and preservation.The device for non-linear optical that the boronic acid compound caesium zinc non-linear optic crystal adopting the method for the invention to obtain is made, at room temperature, light source is made with Nd:YAG Q-switched laser, incident wavelength is the infrared light of 1064nm, output wavelength is the green laser of 532nm, and laser intensity is equivalent to KDP (KH 2pO 4) 3 times.
Accompanying drawing explanation
Fig. 1 is Cs of the present invention 3zn 6b 9o 21the X-ray diffraction figure of powder.
Fig. 2 is Cs of the present invention 3zn 6b 9o 21the fundamental diagram of the device for non-linear optical that crystal makes, wherein 1 is laser apparatus, and 2 for sending light beam, and 3 is Cs 3zn 6b 9o 21crystal, 4 is outgoing beam, and 5 is filter plate.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail:
Embodiment 1:
By reaction formula: 3Cs 2cO 3+ 12ZnO+18H 3bO 3→ 2Cs 3zn 6b 9o 21+ 3CO 2↑+27H 2o ↑ synthesis Cs 3zn 6b 9o 21compound:
By Cs 2cO 3, ZnO, H 3bO 3take put into mortar at 1: 4: 6 in molar ratio, mixing is also carefully ground, then load in the opening corundum crucible of Φ 100mm × 100mm, put into retort furnace, slowly be warming up to 300 DEG C, constant temperature 24 hours, be cooled to room temperature, take out and put into retort furnace after second time grinding, be warming up to 750 DEG C again, constant temperature 24 hours, be cooled to room temperature, take out and put into retort furnace after third time grinding, again 750 DEG C of constant temperature 48 hours, take out through grinding obtained boric acid caesium zn cpds single-phase polycrystalline powder, X-ray analysis is carried out to this product, gained X-ray spectrogram and boric acid caesium zinc Cs 3zn 6b 9o 21the X-ray spectrogram that single crystal structure obtains is consistent,
By the boric acid caesium zinc Cs obtained 3zn 6b 9o 21compound single-phase polycrystal powder and fusing assistant CsF-H 3bO 3cs in molar ratio 3zn 6b 9o 21: CsF-B 2o 3=1: 3, wherein CsF and B 2o 3mol ratio be 3: 5, carry out mixture, load in the opening platinum crucible of Φ 80mm × 80mm, be heated to 750 DEG C with the temperature rise rate of temperature 30 DEG C/h, constant temperature 15 hours, obtains mixed molten liquid, then is cooled to 650 DEG C;
With the speed slow cooling of temperature 0.5 DEG C/h to room temperature, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
Growing crystal in compound liquation: by the Cs obtained 3zn 6b 9o 21seed crystal is fixed on from seed crystal crystal growing furnace top on seed rod, and first at mixed molten liquid preheating seed crystal 10 minutes on the surface, in immersed in liquid level, make seed crystal carry out melt back in mixed molten liquid, constant temperature 30 minutes, fast cooling is to temperature of saturation 650 DEG C;
Again with the cooling of the speed of temperature 2 DEG C of/day, with the rotating speed rotary seed crystal rod of 10rpm, after crystal growth terminates, make crystal depart from liquid level, be down to room temperature with the speed of temperature 10 DEG C/h, the Cs being of a size of 56mm × 40mm × 30mm can be obtained 3zn 6b 9o 21crystal.
Oxide spinel caesium in reaction formula can be replaced with Cs2O or cesium nitrate or cesium oxalate or cesium hydroxide or cesium bicarbonate, and zinc oxide can be replaced with zinc carbonate or zinc nitrate or zinc oxalate or zinc hydroxide or zinc chloride, and boric acid can be replaced by boron oxide.
Embodiment 2:
By reaction formula: 6CsNO 3+ 12ZnO+18H 3bO 3→ 2Cs 3zn 6b 9o 21+ 6NO 2↑+27H 2o ↑+3O 2↑ synthesis Cs 3zn 6b 9o 21compound:
By CsNO 3, ZnO, H 3bO 3directly take raw material at 1: 2: 3 in molar ratio, by the raw material that takes and fusing assistant Cs 2o-B 2o 3carry out mixture at 1: 4 in molar ratio, wherein Cs 2o and B 2o 3mol ratio be 3: 5, load in the opening platinum crucible of Φ 80mm × 80mm, be warming up to temperature 800 DEG C, constant temperature 60 hours, obtains mixed molten liquid, is cooling to temperature 650 DEG C;
With the speed slow cooling of temperature 1.5 DEG C/h to room temperature, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
By the Cs obtained 3zn 6b 9o 21seed crystal is fixed on from seed crystal crystal growing furnace top on seed rod, and first at mixed molten liquid preheating seed crystal 10 minutes on the surface, under immersed in liquid level, make seed crystal carry out melt back in mixed molten liquid, constant temperature 30 minutes, fast cooling is to temperature of saturation 600 DEG C;
Again with the speed slow cooling of temperature 1 DEG C/day, non rotating seed rod, arrives after required yardstick until crystal growth, by crystal lift-off molten surface, be down to room temperature with temperature 20 DEG C/h speed, then crystal taken out from burner hearth, the Cs being of a size of 36mm × 22mm × 15mm can be obtained 3zn 6b 9o 21crystal.
Raw material cesium nitrate in reaction formula can be replaced with Cs2O or cesium carbonate or cesium oxalate or cesium hydroxide or cesium bicarbonate, and zinc oxide can be replaced with zinc carbonate or zinc nitrate or zinc oxalate or zinc hydroxide or zinc chloride, and boric acid can be replaced by boron oxide.
Embodiment 3:
By reaction formula: 6CsHCO 3+ 12ZnO+18H 3bO 3→ 2Cs 3zn 6b 9o 21+ 6CO 2↑+27H 2o ↑ synthesis Cs2 (HCO 3) 2compound:
By Cs2 (HCO 3) 2, ZnO, H 3bO 3directly take raw material at 1: 2: 3 in molar ratio, by the raw material that takes and fusing assistant CsF-PbO in molar ratio 1: 3, carry out mixture, wherein CsF and PbO mol ratio is 3: 1, load in the opening platinum crucible of Φ 80mm × 80mm, be warming up to temperature 780 DEG C, constant temperature 60 hours, obtain mixed molten liquid, then be down to temperature 620 DEG C;
With the speed slow cooling of temperature 3.5 DEG C/h to room temperature, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
By the Cs obtained 3zn 6b 9o 21seed crystal is fixed on from seed crystal crystal growing furnace top on seed rod, and first at mixed molten liquid preheating seed crystal 15 minutes on the surface, under immersed in liquid level, make seed crystal carry out melt back in mixed molten liquid, constant temperature 30 minutes, fast cooling is to temperature of saturation 615 DEG C;
Again with the speed slow cooling of temperature 3 DEG C/day, rotate seed crystal crucible with the rotating speed of 5rpm, arrive after required yardstick until crystal growth, by crystal lift-off molten surface, be down to room temperature with temperature 1 DEG C/h speed, then crystal taken out from burner hearth, the Cs being of a size of 25mm × 24mm × 10mm can be obtained 3zn 6b 9o 21crystal.
Oxide spinel hydrogen caesium in reaction formula can be replaced with cesium carbonate or cesium nitrate or cesium oxalate or cesium hydroxide or Cs2O, and zinc oxide can be replaced with zinc carbonate or zinc nitrate or zinc oxalate or zinc hydroxide or zinc chloride, and boric acid can be replaced by boron oxide.
Embodiment 4:
By reaction formula: 3Cs 2cO 3+ 12ZnO+9B 2o 3→ 2Cs 3zn 6b 9o 21+ 3CO 2↑ synthesis Cs 3zn 6b 9o 21compound:
By Cs 2cO 3, ZnO, B 2o 3directly take raw material at 1: 4: 3 in molar ratio, by the raw material that takes and fusing assistant B 2o 3-PbO carries out mixture, wherein B in molar ratio at 1: 3 2o 3be 5: 1 with PbO mol ratio, load in the opening platinum crucible of Φ 80mm × 80mm, be warming up to temperature 750 DEG C, constant temperature 80 hours, obtains mixed molten liquid, then is down to temperature 615 DEG C;
With the speed slow cooling of temperature 5 DEG C/h to room temperature, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
By the Cs obtained 3zn 6b 9o 21seed crystal is fixed on from seed crystal crystal growing furnace top on seed rod, and first at mixed molten liquid preheating seed crystal 20 minutes on the surface, under immersed in liquid level, make seed crystal carry out melt back in mixed molten liquid, constant temperature 5 minutes, fast cooling is to temperature of saturation 600 DEG C;
Then with the speed slow cooling of temperature 3 DEG C/day, with the rotating speed rotary seed crystal rod of 15rpm, arrive after required yardstick until crystal growth, by crystals from molten surface, be down to room temperature with temperature 15 DEG C/h speed, then crystal taken out from burner hearth, the Cs being of a size of 35mm × 25mm × 20mm can be obtained 3zn 6b 9o 21crystal.
Material oxidation caesium in reaction formula can be replaced with cesium carbonate or cesium nitrate or cesium oxalate or cesium hydroxide or cesium bicarbonate, and zinc oxide can be replaced with zinc carbonate or zinc nitrate or zinc oxalate or zinc hydroxide or zinc chloride, and boron oxide can be replaced by boric acid.
Embodiment 5
By reaction formula: 6CsNO 3+ 12ZnO+9B 2o 3→ 2Cs 3zn 6b 9o 21+ 6NO 2↑+3O 2↑ synthesis Cs 3zn 6b 9o 21compound;
By CsNO 3, ZnO, B 2o 3directly take raw material at 2: 4: 3 in molar ratio, the raw material taken and fusing assistant CsF-PbO are carried out mixture in molar ratio at 1: 2, wherein CsF and PbO mol ratio is in the opening platinum crucible of 5: 1 loading Φ 80mm × 80mm, be warming up to temperature 760 DEG C, constant temperature 80 hours, obtain mixed molten liquid, then be down to temperature 650 DEG C;
With the speed slow cooling of temperature 10 DEG C/h to room temperature, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
The seed crystal of acquisition is fixed on seed rod from seed crystal crystal growing furnace top, first at mixed molten liquid preheating seed crystal 25 minutes on the surface, under part immersed in liquid level, seed crystal is made to carry out melt back in mixed molten liquid, constant temperature 25 minutes, fast cooling is to temperature of saturation 615 DEG C;
Again with the cooling of the speed of temperature 5 DEG C of/day, with the rotating speed rotary seed crystal rod of 30rpm, arrive after required yardstick until crystal growth, by crystal lift-off molten surface, be down to room temperature with temperature 35 DEG C/h speed, then crystal taken out from burner hearth, the Cs being of a size of 22mm × 32mm × 20mm can be obtained 3zn 6b 9o 21crystal.
Raw material cesium nitrate in reaction formula can be replaced with cesium bicarbonate or cesium carbonate or cesium oxalate or cesium hydroxide or Cs2O, and zinc oxide can be replaced with zinc carbonate or zinc nitrate or zinc oxalate or zinc hydroxide or zinc chloride, and boron oxide can be replaced by boric acid.
Embodiment 6
By reaction formula: 6CsHCO 3+ 12ZnO+9B 2o 3→ 2Cs 3zn 6b 9o 21+ 6CO 2↑+3H 2o ↑ synthesis Cs 3zn 6b 9o 21compound:
By CsHCO 3, ZnO, B 2o 3directly take raw material at 2: 4: 3 in molar ratio, the raw material taken and fusing assistant CsF-PbO are carried out mixture in molar ratio at 1: 3, wherein CsF and PbO mol ratio is 5: 1, load in the opening platinum crucible of Φ 80mm × 80mm, be warming up to temperature 800 DEG C, constant temperature obtains mixed molten liquid in 5 hours, then is down to temperature 620 DEG C;
With the speed slow cooling of temperature 4.0 DEG C/h to room temperature, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
By the Cs obtained 3zn 6b 9o 21seed crystal is fixed on from seed crystal crystal growing furnace top on seed rod, and first at mixed molten liquid preheating seed crystal 20 minutes on the surface, under immersed in liquid level, make seed crystal carry out melt back in mixed molten liquid, constant temperature 25 minutes, fast cooling is to temperature of saturation 605 DEG C;
Then with the cooling of the speed of temperature 3 DEG C of/day, with the rotating speed rotary seed crystal rod of 50rpm, arrive after required yardstick until crystal growth, by crystals from molten surface, be down to room temperature with temperature 70 C/h speed, then crystal taken out from burner hearth, the Cs being of a size of 22mm × 21mm × 16mm can be obtained 3zn 6b 9o 21crystal.
Oxide spinel hydrogen caesium in reaction formula can be replaced with cesium carbonate or cesium hydroxide or cesium oxalate or cesium nitrate or Cs2O, and zinc oxide can be replaced with zinc carbonate or zinc nitrate or zinc oxalate or zinc hydroxide or zinc chloride, and boron oxide can be replaced by boric acid;
Embodiment 7
By reaction formula: 3Cs 2c 2o 4+ 12ZnO+9B 2o 3→ 2Cs 3zn 6b 9o 21+ 2CO 2↑+4CO ↑ synthesis Cs 3zn 6b 9o 21compound:
By Cs 2c 2o 4, ZnO, B 2o 3put into mortar at 1: 4: 3 in molar ratio, 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 temperature 500 DEG C, constant temperature 4 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 750 DEG C constant temperature 48 hours again in retort furnace, taken out, put into mortar and smash grinding to pieces and namely obtain Cs 3zn 6b 9o 21compound, carries out X-ray analysis to this product, gained X-ray spectrogram and boric acid caesium zinc Cs 3zn 6b 9o 21the X-ray spectrogram that single crystal structure obtains is consistent;
By the Cs of synthesis 3zn 6b 9o 21compound and fusing assistant Cs 2o-PbO carries out mixture, wherein Cs in molar ratio at 1: 3 2o and PbO mol ratio is 5: 1, and load in the opening platinum crucible of Φ 80mm × 80mm, be warming up to temperature 900 DEG C, constant temperature obtains mixed molten liquid in 50 hours, then is down to temperature 750 DEG C;
With the speed slow cooling of temperature 4.0 DEG C/h to room temperature, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
By the Cs obtained 3zn 6b 9o 21seed crystal is fixed on from seed crystal crystal growing furnace top on seed rod, first at mixed molten liquid preheating seed crystal 20 minutes on the surface, under immersed in liquid level, makes seed crystal carry out melt back in mixed molten liquid, constant temperature 25 minutes, is cooled to temperature of saturation 715 DEG C;
Then with the cooling of the speed of temperature 2 DEG C of/day, with the rotating speed rotary seed crystal rod of 28rpm, arrive after required yardstick until crystal growth, by crystals from molten surface, be down to room temperature with temperature 25 DEG C/h speed, then crystal taken out from burner hearth, the Cs being of a size of 30mm × 22mm × 15mm can be obtained 3zn 6b 9o 21crystal.
Raw material cesium oxalate in reaction formula can be replaced with cesium carbonate or cesium hydroxide or cesium bicarbonate or cesium nitrate or Cs2O, and zinc oxide can be replaced with zinc carbonate or zinc nitrate or zinc oxalate or zinc hydroxide or zinc chloride, and boron oxide can be replaced by boric acid;
Embodiment 8
By reaction formula: 6CsCl+12ZnO+9B 2o 3→ 2Cs 3zn 6b 9o 21+ 3Cl 2↑ synthesis Cs 3zn 6b 9o 21compound:
By CsCl, ZnO, B 2o 3put into mortar at 2: 4: 3 in molar ratio, by the raw material that takes and fusing assistant H 3bO 3-Cs 2o-PbO carries out mixture, wherein B in molar ratio at 1: 1 2o 3, Cs 2o and PbO mol ratio is 6: 3: 4, and load in the opening platinum crucible of Φ 80mm × 80mm, be warming up to temperature 760 DEG C, constant temperature 80 hours, obtains mixed molten liquid, then is down to temperature 650 DEG C;
With the speed slow cooling of temperature 10 DEG C/h to room temperature, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
The seed crystal of acquisition is fixed on seed rod from seed crystal crystal growing furnace top, first at mixed molten liquid preheating seed crystal 25 minutes on the surface, under part immersed in liquid level, seed crystal is made to carry out melt back in mixed molten liquid, constant temperature 25 minutes, fast cooling is to temperature of saturation 615 DEG C;
Again with the cooling of the speed of temperature 5 DEG C of/day, with the rotating speed rotary seed crystal rod of 30rpm, arrive after required yardstick until crystal growth, by crystal lift-off molten surface, be down to room temperature with temperature 35 DEG C/h speed, then crystal taken out from burner hearth, the Cs being of a size of 22mm × 32mm × 20mm can be obtained 3zn 6b 9o 21crystal.
Raw material cesium chloride in reaction formula can be replaced with cesium carbonate or cesium hydroxide or cesium oxalate or cesium nitrate or Cs2O, and zinc oxide can be replaced with zinc carbonate or zinc nitrate or zinc oxalate or zinc hydroxide or zinc chloride, and boron oxide can be replaced by boric acid;
Embodiment 9
By arbitrary for embodiment 1-8 gained Cs 3zn 6b 9o 21crystal processes the frequency doubling device of one piece of size 5mm × 5mm × 6mm by the direction that matches, be placed on the position of 3 by shown in accompanying drawing 2, at room temperature, with tune QNd:YAG laser light source, incident wavelength is 1064nm, and sending wavelength by adjusting QNd:YAG laser apparatus 1 is that Cs injected by the infrared beam 2 of 1064nm 3zn 6b 9o 21monocrystalline 3, produce the green frequency doubled light that wavelength is 532nm, output intensity is 5 times of equal conditions KDP, and outgoing beam 4 is the infrared light of 1064nm and the green glow of 532nm containing wavelength, after filter plate 5 elimination, obtain the green laser that wavelength is 532nm.

Claims (7)

1. a boronic acid compound caesium zinc, is characterized in that the chemical formula of this compound is Cs 3zn 6b 9o 21, molecular weight 1224.24, adopts solid reaction process synthetic compound.
2. a boronic acid compound caesium zinc non-linear optic crystal, is characterized in that the chemical formula of this crystal is Cs 3zn 6b 9o 21, molecular weight 1224.24, does not have symmetry centre, belongs to rhombic system, spacer Cmc2 1, unit cell parameters is z=4,
3. a preparation method for boronic acid compound caesium zinc non-linear optic crystal according to claim 2, it is characterized in that adopting solid reaction process synthetic compound and high temperature solution method growth boric acid caesium zinc non-linear optic crystal, concrete operations follow these steps to carry out:
A, boric acid caesium zn cpds single-phase polycrystalline powder to be mixed with fusing assistant, temperature 650-1000 DEG C is heated to the temperature rise rate of temperature 1-30 DEG C/h, constant temperature 5-80 hour, obtain mixed molten liquid, be cooled to temperature 500-800 DEG C again, obtain mixed molten liquid, the mol ratio of its mesoboric acid caesium zn cpds single-phase polycrystalline powder and fusing assistant is 1: 1-10;
Or directly will mix with fusing assistant containing Cesium compound, zinc compound and boric acid, temperature 650-1000 DEG C is heated to the temperature rise rate of temperature 1-30 DEG C/h, constant temperature 5-80 hour, obtain mixed molten liquid, be cooled to temperature 500-800 DEG C again, obtain mixed molten liquid, the mol ratio wherein containing Cesium compound, zinc compound and boric acid and fusing assistant is 3: 6: 9: 1-10;
B, prepare boric acid caesium zinc seed crystal: the mixed molten liquid obtained by step a is slowly down to room temperature with the speed of temperature 0.5-10 DEG C/h, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
C, the crucible filling the mixed molten liquid that step a obtains is inserted in crystal growing furnace, the seed crystal obtained by step b is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 5-60 minute, seed crystal is carried out melt back in contact mixed molten liquid liquid level or mixed molten liquid, constant temperature 5-60 minute, is down to temperature of saturation with the speed of temperature 1-60 DEG C/h;
D, again with the speed slow cooling of temperature 0.1-5 DEG C/day, the growth of crystal is carried out with 0-60rpm rotating speed rotary seed crystal rod, arrive after required yardstick until single crystal growing, by crystal lift-off mixed molten liquid surface, and be down to room temperature with temperature 1-80 DEG C/h speed, then crystal is taken out from burner hearth, boric acid caesium zinc non-linear optic crystal can be obtained.
4. method according to claim 3, to is characterized in that described in step a containing Cesium compound being Cs 2o, CsF, CsCl, Cs 2cO 3, CsNO 3, CsOH, Cs 2c 2o 4h 2o or Cs 2c 2h 3o 2, zinc compound is ZnO, Zn (NO 3) 2, ZnCO 3, ZnC 2h 3o 2, Zn (OH) 2or ZnCl 2.
5. method according to claim 4, is characterized in that fusing assistant described in step a is Cs 2o-B 2o 3, Cs 2o-PbO, CsF-B 2o 3, CsF-PbO, B 2o 3-PbO or B 2o 3-PbO-Cs 2o.
6. method according to claim 5, is characterized in that fusing assistant Cs 2o-B 2o 3cs in system 2o and B 2o 3mol ratio be 1-3: 2-5; Cs 2cs in O-PbO system 2o and PbO mol ratio is 1-3: 3-6; CsF-B 2o 3csF and B in system 2o 3mol ratio be 1-6: 2-5; In CsF-PbO system, CsF and PbO mol ratio is 1-6: 3-6; B 2o 3b in-PbO system 2o 3be 2-5: 1-3 with PbO mol ratio; B 2o 3-PbO-Cs 2b in O system 2o 3, Cs 2o and PbO mol ratio is 2-5: 1-6: 3-8.
7. a purposes for boric acid caesium zinc non-linear optic crystal according to claim 2, is characterized in that, this boric acid caesium zinc non-linear optic crystal is for the preparation of doubly frequency generator, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
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CN103588218B (en) * 2013-10-21 2017-10-03 中国科学院福建物质结构研究所 CsZn2B3O7Compound, CsZn2B3O7Nonlinear optical crystal and its preparation method and purposes
CN106978627B (en) * 2017-03-29 2019-03-12 中国科学院新疆理化技术研究所 Lithium borate zinc phase-change material and its preparation method and application
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101311370A (en) * 2008-04-17 2008-11-26 中国科学院新疆理化技术研究所 Large-sized bismuth zinc borate nonlinear optical crystal, preparation method and use
CN101851784A (en) * 2010-04-01 2010-10-06 中国科学院新疆理化技术研究所 Compound cesium lithium borate nonlinear optical crystal and making method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101311370A (en) * 2008-04-17 2008-11-26 中国科学院新疆理化技术研究所 Large-sized bismuth zinc borate nonlinear optical crystal, preparation method and use
CN101851784A (en) * 2010-04-01 2010-10-06 中国科学院新疆理化技术研究所 Compound cesium lithium borate nonlinear optical crystal and making method and application thereof

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