CN103590107A - Compound caesium zinc borate, and caesium zinc borate nonlinear optical crystal and preparation method and application thereof - Google Patents

Compound caesium zinc borate, and caesium zinc borate nonlinear optical crystal and preparation method and application thereof Download PDF

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CN103590107A
CN103590107A CN201210293692.4A CN201210293692A CN103590107A CN 103590107 A CN103590107 A CN 103590107A CN 201210293692 A CN201210293692 A CN 201210293692A CN 103590107 A CN103590107 A CN 103590107A
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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 nonlinear optical crystals and Preparation method and use, the chemical formula of the boronic acid compound caesium zinc is Cs3Zn6B9O21, molecular weight 1224.24, the chemical formula of boronic acid compound caesium zinc nonlinear optical crystal is Cs3Zn6B9O21, molecular weight 1224.24, belong to rhombic system, space group Cmc21, cell parameter is
Figure DSA00000764991300011
Figure DSA00000764991300012
Its powder SHG effect reaches 3 times of KDP (KH2PO4), and boronic acid compound caesium zinc is synthesized using solid reaction process; Boric acid caesium zinc nonlinear optical crystal is grown using high temperature solution method, the boric acid caesium zinc nonlinear optical crystal mechanical hardness is big, easy to cut, polishing and preservation are used widely in the device for non-linear optical such as preparation times frequency generator, upper frequency converter, lower frequency converter or optical parametric oscillator.

Description

Compound boric acid 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 21compound boric acid caesium zinc and boric acid caesium zinc non-linear optic crystal, the preparation method of crystal and the device for non-linear optical that utilizes this crystal to make.
Background technology
Non-linear optical crystal material is one of important photoelectric information functional material, be the particularly important substance basis of laser technology of photoelectron technology, in fields such as information, the energy, industrial manufacture, medical science, scientific research, military affairs, be with a wide range of applications and huge using value.Each developed country of the world is all placed on the position of first developing by the research of novel nonlinear optical crystal material, and lists in the research project of every country as a grand strategy measure.
Borate crystal is because its band gap is larger, and two-photon absorption probability is little, and laser damage threshold is higher, is beneficial to the stronger non-linear optical effect of acquisition, 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 further increase frequency-doubled effect.Therefore, transition metal is boratory synthetic by the effective means that is the large frequency-doubled effect ultraviolet nonlinear optical material of design.
Summary of the invention
The object of the invention is to provide a kind of compound boric acid 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 who adopts 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 frequency multiplication producer, upper or lower frequency transmodulator or optical parametric oscillator.
A kind of compound boric acid 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 boric acid 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
Figure BSA00000764991600021
z=4,
Figure BSA00000764991600022
Figure BSA00000764991600023
its powder SHG effect reaches KDP (KH 2pO 4) 3 times.
The preparation method of described boric acid caesium zinc non-linear optic crystal, adopts solid reaction process synthetic compound and high temperature solution method growth boric acid caesium zinc non-linear optic crystal, and concrete operations follow these steps to carry out:
A, boric acid caesium zn cpds single-phase polycrystalline powder is evenly mixed with fusing assistant, temperature rise rate with temperature 1-30 ℃/h is heated to temperature 650-1000 ℃, constant temperature 5-80 hour, obtain mixed molten liquid, be cooled to temperature 500-800 ℃, the mol ratio of its mesoboric acid caesium zn cpds single-phase polycrystalline powder and fusing assistant is 1: 1-6 again;
Or directly will mix with fusing assistant containing Cesium compound, zinc compound and boric acid, temperature rise rate with temperature 1-30 ℃/h is heated to temperature 650-1000 ℃, constant temperature 5-80 hour, obtain mixed molten liquid, be cooled to temperature 500-800 ℃, wherein the mol ratio containing Cesium compound, zinc compound and boric acid and fusing assistant is 1-2: 2-4: 3-6: 1-18 again;
B, prepare boric acid caesium zinc seed crystal: the mixed molten liquid that step a is obtained is slowly down to room temperature with the speed of temperature 3-10 ℃/h, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
C, the crucible that fills the mixed molten liquid that step a makes is inserted in crystal growing furnace, the seed crystal that step b is obtained is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 5-60 minute, seed crystal is carried out to 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 ℃/h;
D, again with the speed slow cooling of temperature 0.1-5 ℃/day, with 0-60rpm rotating speed rotary seed crystal rod, carry out the growth of crystal, after required yardstick is arrived in single crystal growing, crystal is lifted to mixed molten liquid surface, and be down to room temperature with temperature 1-80 ℃/h speed, then crystal is taken out from burner hearth, can obtain boric acid caesium zinc non-linear optic crystal.
In boric acid caesium zinc described in step a, containing Cesium compound, be 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.
Described in step a, fusing assistant 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 are 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 are 1-6: 3-8; B 2o 3b in-PbO system 2o 3with PbO mol ratio be 2-5: 3-8; B 2o 3-PbO-Cs 2b in O system 2o 3, Cs 2o and PbO mol ratio are 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 frequency multiplication producer, 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↑
The crystal that obtains has wider transmission region, and hardness is larger, 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 compound boric acid caesium zinc non-linear optic crystal that adopts the method for the invention to obtain is made, at room temperature, with Nd:YAG Q-switched laser, make light source, 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 is made, wherein 1 is laser apparatus, and 2 for sending light beam, and 3 is Cs 3zn 6b 9o 21crystal, 4 is outgoing beam, 5 is filter plate.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail:
Embodiment 1:
Press reaction formula: 3Cs 2cO 3+ 12ZnO+18H 3bO 3→ 2Cs 3zn 6b 9o 21+ 3CO 2↑+27H 2o ↑ synthetic Cs 3zn 6b 9o 21compound:
By Cs 2cO 3, ZnO, H 3bO 3within 1: 4: 6 in molar ratio, take and put into mortar, mix and carefully grind, then pack in the opening corundum crucible of Φ 100mm * 100mm, put into retort furnace, slowly be warming up to 300 ℃, constant temperature 24 hours, be cooled to room temperature, taking-up is put into retort furnace after grinding for the second time, be warming up to again 750 ℃, constant temperature 24 hours, be cooled to room temperature, taking-up is put into retort furnace after grinding for the third time, again 750 ℃ of constant temperature 48 hours, taking-up makes boric acid caesium zn cpds single-phase polycrystalline powder through grinding, this product is carried out to X-ray analysis, 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 obtaining 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, be mixed, pack in the opening platinum crucible of Φ 80mm * 80mm, with the temperature rise rate of 30 ℃/h of temperature, be heated to 750 ℃, constant temperature 15 hours, obtains mixed molten liquid, then is cooled to 650 ℃;
With the speed slow cooling of 0.5 ℃/h of temperature, to room temperature, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
Growing crystal in compound liquation: by the Cs obtaining 3zn 6b 9o 21seed crystal is fixed on seed rod seed crystal from crystal growing furnace top, and first preheating seed crystal 10 minutes on mixed molten liquid surface, in immersed in liquid level, makes seed crystal in mixed molten liquid, carry out melt back, constant temperature 30 minutes, and fast cooling is to 650 ℃ of temperature of saturation;
With the speed cooling of 2 ℃/day of temperature, with the rotating speed rotary seed crystal rod of 10rpm, after crystal growth finishes, make crystal depart from liquid level again, with the speed of 10 ℃/h of temperature, be down to room temperature, can obtain the Cs that is of a size of 56mm * 40mm * 30mm 3zn 6b 9o 21crystal.
Raw material cesium carbonate 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:
Press reaction formula: 6CsNO 3+ 12ZnO+18H 3bO 3→ 2Cs 3zn 6b 9o 21+ 6NO 2↑+27H 2o ↑+3O 2↑ synthetic Cs 3zn 6b 9o 21compound:
By CsNO 3, ZnO, H 3bO 3within 1: 2: 3 in molar ratio, directly take raw material, by the raw material taking and fusing assistant Cs 2o-B 2o 3within 1: 4 in molar ratio, be mixed, wherein Cs 2o and B 2o 3mol ratio be 3: 5, pack in the opening platinum crucible of Φ 80mm * 80mm, be warming up to 800 ℃ of temperature, constant temperature 60 hours, obtains mixed molten liquid, is cooling to 650 ℃ of temperature;
With the speed slow cooling of 1.5 ℃/h of temperature, to room temperature, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
By the Cs obtaining 3zn 6b 9o 21seed crystal is fixed on seed rod seed crystal from crystal growing furnace top, and first preheating seed crystal 10 minutes on mixed molten liquid surface, under immersed in liquid level, makes seed crystal in mixed molten liquid, carry out melt back, constant temperature 30 minutes, and fast cooling is to 600 ℃ of temperature of saturation;
Again with the speed slow cooling of 1 ℃/day of temperature, rotary seed crystal rod not, after crystal grows into required yardstick, crystal is lifted to molten surface, with 20 ℃/h of temperature speed, be down to room temperature, then crystal taken out from burner hearth, can obtain the Cs that is of a size of 36mm * 22mm * 15mm 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:
Press reaction formula: 6CsHCO 3+ 12ZnO+18H 3bO 3→ 2Cs 3zn 6b 9o 21+ 6CO 2↑+27H 2o ↑ synthetic Cs2 (HCO 3) 2compound:
By Cs2 (HCO 3) 2, ZnO, H 3bO 3within 1: 2: 3 in molar ratio, directly take raw material, by the raw material taking and fusing assistant CsF-PbO 1: 3 in molar ratio, be mixed, wherein CsF and PbO mol ratio are 3: 1, pack in the opening platinum crucible of Φ 80mm * 80mm, be warming up to 780 ℃ of temperature, constant temperature 60 hours, obtain mixed molten liquid, then be down to 620 ℃ of temperature;
With the speed slow cooling of 3.5 ℃/h of temperature, to room temperature, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
By the Cs obtaining 3zn 6b 9o 21seed crystal is fixed on seed rod seed crystal from crystal growing furnace top, and first preheating seed crystal 15 minutes on mixed molten liquid surface, under immersed in liquid level, makes seed crystal in mixed molten liquid, carry out melt back, constant temperature 30 minutes, and fast cooling is to 615 ℃ of temperature of saturation;
Again with the speed slow cooling of 3 ℃/day of temperature, with the rotating speed rotation seed crystal crucible of 5rpm, after crystal grows into required yardstick, crystal is lifted to molten surface, with 1 ℃/h of temperature speed, be down to room temperature, then crystal taken out from burner hearth, can obtain the Cs that is of a size of 25mm * 24mm * 10mm 3zn 6b 9o 21crystal.
Raw material cesium bicarbonate 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:
Press reaction formula: 3Cs 2cO 3+ 12ZnO+9B 2o 3→ 2Cs 3zn 6b 9o 21+ 3CO 2↑ synthetic Cs 3zn 6b 9o 21compound:
By Cs 2cO 3, ZnO, B 2o 3within 1: 4: 3 in molar ratio, directly take raw material, by the raw material taking and fusing assistant B 2o 3-PbO is mixed for 1: 3 in molar ratio, wherein B 2o 3with PbO mol ratio be 5: 1, pack in the opening platinum crucible of Φ 80mm * 80mm, be warming up to 750 ℃ of temperature, constant temperature 80 hours, obtains mixed molten liquid, then is down to 615 ℃ of temperature;
With the speed slow cooling of 5 ℃/h of temperature, to room temperature, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
By the Cs obtaining 3zn 6b 9o 21seed crystal is fixed on seed rod seed crystal from crystal growing furnace top, and first preheating seed crystal 20 minutes on mixed molten liquid surface, under immersed in liquid level, makes seed crystal in mixed molten liquid, carry out melt back, constant temperature 5 minutes, and fast cooling is to 600 ℃ of temperature of saturation;
Then with the speed slow cooling of 3 ℃/day of temperature, with the rotating speed rotary seed crystal rod of 15rpm, after crystal grows into required yardstick, by crystal body from molten surface, with 15 ℃/h of temperature speed, be down to room temperature, then crystal taken out from burner hearth, can obtain the Cs that is of a size of 35mm * 25mm * 20mm 3zn 6b 9o 21crystal.
Raw material Cs2O 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
Press reaction formula: 6CsNO 3+ 12ZnO+9B 2o 3→ 2Cs 3zn 6b 9o 21+ 6NO 2↑+3O 2↑ synthetic Cs 3zn 6b 9o 21compound;
By CsNO 3, ZnO, B 2o 3within 2: 4: 3 in molar ratio, directly take raw material, the raw material taking and fusing assistant CsF-PbO are mixed for 1: 2 in molar ratio, wherein CsF and PbO mol ratio are to pack at 5: 1 in the opening platinum crucible of Φ 80mm * 80mm, be warming up to 760 ℃ of temperature, constant temperature 80 hours, obtain mixed molten liquid, then be down to 650 ℃ of temperature;
With the speed slow cooling of 10 ℃/h of temperature, to room temperature, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
The seed crystal of acquisition is fixed on seed rod to seed crystal from crystal growing furnace top, first preheating seed crystal 25 minutes on mixed molten liquid surface, under part immersed in liquid level, makes seed crystal in mixed molten liquid, carry out melt back, constant temperature 25 minutes, fast cooling is to 615 ℃ of temperature of saturation;
With the speed of 5 ℃/day of temperature, lower the temperature again, with the rotating speed rotary seed crystal rod of 30rpm, after crystal grows into required yardstick, crystal is lifted to molten surface, with 35 ℃/h of temperature speed, be down to room temperature, then crystal taken out from burner hearth, can obtain the Cs that is of a size of 22mm * 32mm * 20mm 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
Press reaction formula: 6CsHCO 3+ 12ZnO+9B 2o 3→ 2Cs 3zn 6b 9o 21+ 6CO 2↑+3H 2o ↑ synthetic Cs 3zn 6b 9o 21compound:
By CsHCO 3, ZnO, B 2o 3within 2: 4: 3 in molar ratio, directly take raw material, the raw material taking and fusing assistant CsF-PbO are mixed for 1: 3 in molar ratio, wherein CsF and PbO mol ratio are 5: 1, pack in the opening platinum crucible of Φ 80mm * 80mm, be warming up to 800 ℃ of temperature, constant temperature obtains mixed molten liquid in 5 hours, then is down to 620 ℃ of temperature;
With the speed slow cooling of 4.0 ℃/h of temperature, to room temperature, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
By the Cs obtaining 3zn 6b 9o 21seed crystal is fixed on seed rod seed crystal from crystal growing furnace top, and first preheating seed crystal 20 minutes on mixed molten liquid surface, under immersed in liquid level, makes seed crystal in mixed molten liquid, carry out melt back, constant temperature 25 minutes, and fast cooling is to 605 ℃ of temperature of saturation;
Then with the speed of 3 ℃/day of temperature, lower the temperature, with the rotating speed rotary seed crystal rod of 50rpm, after crystal grows into required yardstick, by crystal body from molten surface, with temperature 70 C/h speed, be down to room temperature, then crystal taken out from burner hearth, can obtain the Cs that is of a size of 22mm * 21mm * 16mm 3zn 6b 9o 21crystal.
Raw material cesium bicarbonate 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
Press reaction formula: 3Cs 2c 2o 4+ 12ZnO+9B 2o 3→ 2Cs 3zn 6b 9o 21+ 2CO 2↑+4CO ↑ synthetic Cs 3zn 6b 9o 21compound:
By Cs 2c 2o 4, ZnO, B 2o 3within 1: 4: 3 in molar ratio, put into mortar, mix and carefully grind, then pack in the opening corundum crucible of Φ 100mm * 100mm, compressed, put into retort furnace, be slowly warming up to 500 ℃ of temperature, constant temperature 4 hours, take out after cooling crucible, now sample is more loose, then takes out sample and again grinds evenly, be placed in again crucible, in retort furnace, in 750 ℃ of temperature constant temperature 48 hours again, taken out, put into mortar and smash grinding to pieces and 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 synthetic Cs 3zn 6b 9o 21compound and fusing assistant Cs 2o-PbO is mixed for 1: 3 in molar ratio, wherein Cs 2o and PbO mol ratio are 5: 1, pack in the opening platinum crucible of Φ 80mm * 80mm, are warming up to 900 ℃ of temperature, and constant temperature obtains mixed molten liquid in 50 hours, then are down to 750 ℃ of temperature;
With the speed slow cooling of 4.0 ℃/h of temperature, to room temperature, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
By the Cs obtaining 3zn 6b 9o 21seed crystal is fixed on seed rod seed crystal from crystal growing furnace top, and first preheating seed crystal 20 minutes on mixed molten liquid surface, under immersed in liquid level, makes seed crystal in mixed molten liquid, carry out melt back, and constant temperature 25 minutes, is cooled to 715 ℃ of temperature of saturation;
Then with the speed of 2 ℃/day of temperature, lower the temperature, with the rotating speed rotary seed crystal rod of 28rpm, after crystal grows into required yardstick, by crystal body from molten surface, with 25 ℃/h of temperature speed, be down to room temperature, then crystal taken out from burner hearth, can obtain the Cs that is of a size of 30mm * 22mm * 15mm 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
Press reaction formula: 6CsCl+12ZnO+9B 2o 3→ 2Cs 3zn 6b 9o 21+ 3Cl 2↑ synthetic Cs 3zn 6b 9o 21compound:
By CsCl, ZnO, B 2o 3within 2: 4: 3 in molar ratio, put into mortar, by the raw material taking and fusing assistant H 3bO 3-Cs 2o-PbO is mixed for 1: 1 in molar ratio, wherein B 2o 3, Cs 2o and PbO mol ratio are 6: 3: 4, pack in the opening platinum crucible of Φ 80mm * 80mm, are warming up to 760 ℃ of temperature, and constant temperature 80 hours, obtains mixed molten liquid, then are down to 650 ℃ of temperature;
With the speed slow cooling of 10 ℃/h of temperature, to room temperature, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
The seed crystal of acquisition is fixed on seed rod to seed crystal from crystal growing furnace top, first preheating seed crystal 25 minutes on mixed molten liquid surface, under part immersed in liquid level, makes seed crystal in mixed molten liquid, carry out melt back, constant temperature 25 minutes, fast cooling is to 615 ℃ of temperature of saturation;
With the speed of 5 ℃/day of temperature, lower the temperature again, with the rotating speed rotary seed crystal rod of 30rpm, after crystal grows into required yardstick, crystal is lifted to molten surface, with 35 ℃/h of temperature speed, be down to room temperature, then crystal taken out from burner hearth, can obtain the Cs that is of a size of 22mm * 32mm * 20mm 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 embodiment 1-8 gained Cs arbitrarily 3zn 6b 9o 21crystal is by the frequency doubling device of the size 5mm * 5mm * 6mm of direction processing that matches, by being placed in shown in accompanying drawing 2 on 3 position, at room temperature, with adjusting Q Nd:YAG laser apparatus, make light source, incident wavelength is 1064nm, by adjusting Q Nd:YAG laser apparatus 1 to send wavelength, is that the infrared beam 2 of 1064nm is injected Cs 3zn 6b 9o 21monocrystalline 3, the green frequency doubled light that generation wavelength is 532nm, output intensity is 5 times of equal conditions KDP, it is the infrared light of 1064nm and the green glow of 532nm that outgoing beam 4 contains wavelength, obtains the green laser that wavelength is 532nm after filter plate 5 eliminations.

Claims (7)

1. a compound boric acid caesium zinc, the chemical formula that it is characterized in that this compound is Cs 3zn 6b 9o 21, molecular weight 1224.24, adopts solid reaction process synthetic compound.
2. a compound boric acid caesium zinc non-linear optic crystal, the chemical formula that it is characterized in that 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
Figure FSA00000764991500011
Figure FSA00000764991500012
z=4,
Figure FSA00000764991500013
3. the preparation method of compound boric acid caesium zinc non-linear optic crystal according to claim 2, is characterized in that adopting solid reaction process synthetic compound and high temperature solution method growth boric acid caesium zinc non-linear optic crystal, and concrete operations follow these steps to carry out:
A, boric acid caesium zn cpds single-phase polycrystalline powder is mixed with fusing assistant, temperature rise rate with temperature 1-30 ℃/h is heated to temperature 650-1000 ℃, constant temperature 5-80 hour, obtain mixed molten liquid, be cooled to temperature 500-800 ℃, the mol ratio of its mesoboric acid caesium zn cpds single-phase polycrystalline powder and fusing assistant is 1: 1-10 again;
Or directly will mix with fusing assistant containing Cesium compound, zinc compound and boric acid, temperature rise rate with temperature 1-30 ℃/h is heated to temperature 650-1000 ℃, constant temperature 5-80 hour, obtain mixed molten liquid, be cooled to temperature 500-800 ℃, wherein the mol ratio containing Cesium compound, zinc compound and boric acid and fusing assistant is 3: 6: 9: 1-10 again;
B, prepare boric acid caesium zinc seed crystal: the mixed molten liquid that step a is obtained is slowly down to room temperature with the speed of temperature 0.5-10 ℃/h, spontaneous crystallization obtains boric acid caesium zinc seed crystal;
C, the crucible that fills the mixed molten liquid that step a makes is inserted in crystal growing furnace, the seed crystal that step b is obtained is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 5-60 minute, seed crystal is carried out to 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 ℃/h;
D, again with the speed slow cooling of temperature 0.1-5 ℃/day, with 0-60rpm rotating speed rotary seed crystal rod, carry out the growth of crystal, after required yardstick is arrived in single crystal growing, crystal is lifted to mixed molten liquid surface, and be down to room temperature with temperature 1-80 ℃/h speed, then crystal is taken out from burner hearth, can obtain boric acid caesium zinc non-linear optic crystal.
4. method according to claim 3, is characterized in that described in step a containing Cesium compound, being Cs in boric acid caesium zinc 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.
5. method according to claim 4, is characterized in that described in step a that fusing assistant 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 are 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 are 1-6: 3-6; H 3bO 3cs in-PbO system 2o and PbO mol ratio are 2-5: 1-3; B 2o 3-PbO-Cs 2b in O system 2o 3, Cs 2o and PbO mol ratio are 2-5: 1-6: 3-8.
7. the purposes of 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 frequency multiplication producer, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
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