CN102978702A - Compound barium borofluoride, barium borofluoride non-linear optical crystal, and preparation method and use of the barium borofluoride non-linear optical crystal - Google Patents

Compound barium borofluoride, barium borofluoride non-linear optical crystal, and preparation method and use of the barium borofluoride non-linear optical crystal Download PDF

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CN102978702A
CN102978702A CN2011102581710A CN201110258171A CN102978702A CN 102978702 A CN102978702 A CN 102978702A CN 2011102581710 A CN2011102581710 A CN 2011102581710A CN 201110258171 A CN201110258171 A CN 201110258171A CN 102978702 A CN102978702 A CN 102978702A
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barium
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fluoborate
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CN102978702B (en
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潘世烈
吴红萍
俞洪伟
侯雪玲
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Abstract

A kind of compound barium fluoborate and barium fluoborate nonlinear optical crystal and preparation method and purposes, compound barium fluoborate and its nonlinear optical crystal chemical formula are Ba3B6O11F2, crystal category monoclinic system, space group P2 (1), and cell parameter is
Figure DSA00000567064800011
Figure DSA00000567064800012
Figure DSA00000567064800013
Beta=101.351 (4) deg.,
Figure DSA00000567064800014
Molecular weight 690.88. Its powder SHG effect reaches 3 times of KDP (KH2PO4), and compound barium fluoborate is synthesized using solid reaction process; Barium fluoborate nonlinear optical crystal is grown using high temperature solution method, the barium fluoborate 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 barium fluoborate and barium fluoborate non-linear optic crystal and preparation method and purposes
Technical field
The present invention relates to chemical formula is Ba 3B 6O 11F 2Compound barium fluoborate and barium fluoborate non-linear optic crystal, crystal preparation method and the device for non-linear optical that utilizes this crystal to make.
Background technology
At present main nonlinear optical material has: BBO (β-BBO), LBO (LiB 3O 5) crystal, CBO (CsB 3O 5) crystal, CLBO (CsLiB 6O 10) crystal and KBBF (KBe 2BO 3F 2) crystal.Although the crystal technique of these materials reaches its maturity, but still exist obvious weak point:, layer growth habit long such as the easy deliquescence of crystal, growth cycle seriously and expensive etc.Therefore, seek new non-linear optical crystal material and remain an extremely important and large order.
Thereby in recent years, when the Development of Novel non-linear optic crystal, not only pay attention to optical property and the mechanical property of crystal, and more and more pay attention to the preparation characteristic of crystal, wish that new crystalline material prepares easily, can obtain the non-linear optic crystal of cheap large-size high-quality.Introduce alkaline earth metal cation and halide-ions with under the design philosophy guidance that improves its performance in boron oxygen framework, negatively charged ion is take boron oxygen functional motif as the basis, and its band gap is larger, and the two-photon absorption probability is little; Laser damage threshold is higher; Be beneficial to the stronger non-linear optical effect of acquisition; The B-O key is beneficial to the wide band light transmission.The cation selective alkaline-earth metal ions, its in the ultraviolet region without d 0The transition of electronics is conducive to ultraviolet and sees through, and its transparency range has been widened in the simultaneously introducing of halide-ions.
Summary of the invention
The object of the invention is to provide a kind of compound barium fluoborate, and the barium fluoborate non-linear optic crystal, and chemical formula is Ba 3B 6O 11F 2
Another purpose of the present invention is to provide the preparation method who adopts solid reaction process synthetic compound and high temperature solution method growth barium fluoborate non-linear optic crystal.
Further object of the present invention provides a kind of purposes of barium fluoborate 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 barium fluoborate of the present invention, the chemical formula of this compound is Ba 3B 6O 11F 2, molecular weight 690.88 adopts the solid reaction process synthetic compound.
A kind of compound barium fluoborate non-linear optic crystal, this crystal-chemical formula is Ba 3B 6O 11F 2, do not have symmetry centre, belong to oblique system, spacer P2 (1), unit cell parameters is
Figure BSA00000567065100021
Figure BSA00000567065100022
Figure BSA00000567065100023
Figure BSA00000567065100024
β=101.351 (4) ° .Z=2,
Figure BSA00000567065100025
Its powder SHG effect reaches KDP (KH 2PO 4) 3 times.
The preparation method of described barium fluoborate non-linear optic crystal adopts solid reaction process synthetic compound and high temperature solution method growth barium fluoborate non-linear optic crystal, and concrete operations follow these steps to carry out:
A, barium fluoborate compound single-phase polycrystal powder is evenly mixed with fusing assistant, temperature rise rate with temperature 1-30 ℃/h is heated to temperature 650-900 ℃, constant temperature 5-80 hour, obtain mixed molten liquid, be cooled to temperature 610-830 ℃, wherein the mol ratio of barium fluoborate compound single-phase polycrystal powder and fusing assistant is 1: 1-6 again;
Or directly containing barium compound, barium fluoride and boric acid and fusing assistant are mixed, temperature rise rate with temperature 1-30 ℃/h is heated to temperature 650-900 ℃, constant temperature 5-80 hour, obtain mixed molten liquid, be cooled to temperature 610-830 ℃, wherein the mol ratio of containing barium compound, barium fluoride and boric acid and fusing assistant is 2: 1: 6: 1-6 again;
B, preparation barium fluoborate seed crystal: the mixed molten liquid that step a obtains slowly is down to room temperature with the speed of temperature 0.5-10 ℃/h, and spontaneous crystallization obtains the barium fluoborate seed crystal;
C, the crucible that will fill the mixed molten liquid that step a makes are inserted in the crystal growing furnace, the seed crystal that step b is obtained is fixed on the seed rod, seed crystal under the crystal growing furnace top, elder generation's 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, be down to temperature of saturation with the speed of temperature 1-60 ℃/h.
D, again with temperature 0.1-5 ℃/day speed slow cooling, carry out the growth of crystal with 0-60rpm rotating speed rotary seed crystal rod, after required yardstick is arrived in single crystal growing, crystal is lifted from the 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 the barium fluoborate non-linear optic crystal.
The described containing barium compound of step a is barium carbonate, nitrate of baryta, barium oxide, hydrated barta, barium bicarbonate or barium oxalate.
The described fusing assistant of step a is NaF-H 3BO 3, H 3BO 3-Na 2O, Na 2O-PbO, LiF-PbO, NaF-PbO or H 3BO 3-PbO.
Fusing assistant NaF-H 3BO 3NaF and H in the system 3BO 3Mol ratio be 1-5: 3-6; The mol ratio of fluorochemical and plumbous oxide is 1-5: 1-6 in LiF-PbO or the NaF-PbO system; H 3BO 3-PbO or H 3BO 3-Na 2The mol ratio of O system mesoboric acid and oxide compound is 2-5: 1-5; Na 2The mol ratio of sodium oxide and plumbous oxide is 1-5: 0.1-6 in the O-PbO system.
The purposes of described barium fluoborate non-linear optic crystal is for the preparation of frequency multiplication producer, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
Barium fluoborate compound provided by the invention, its chemical formula are Ba 3B 6O 11F 2It adopts solid reaction process to prepare the barium fluoborate compound by following chemical equation:
(1)2BaCO 3+BaF 2+6H 3BO 3→Ba 3B 6O 11F 2+2CO 2↑+9H 2O↑
(2)2Ba(NO 3) 2+BaF 2+6H 3BO 3→Ba 3B 6O 11F 2+2NO 2↑+9H 2O↑+3O 2↑
(3)2BaO+BaF 2+6H 3BO 3→Ba 3B 6O 11F 2+9H 2O↑
(4)2Ba(OH) 2+BaF 2+6H 3BO 3→Ba 3B 6O 11F 2+11H 2O↑
(5)2Ba(HCO 3) 2+BaF 2+6H 3BO 3→Ba 3B 6O 11F 2+4CO 2↑+11H 2O↑
(6)2BaCO 3+BaF 2+3B 2O 3→Ba 3B 6O 11F 2+2CO 2↑
(7)2Ba(NO 3) 2+BaF 2+3B 2O 3→Ba 3B 6O 11F 2+4NO 2↑+O 2↑
(8)2BaO+BaF 2+3B 2O 3→Ba 3B 6O 11F 2
(9)2Ba(OH) 2+BaF 2+3B 2O 3→Ba 3B 6O 11F 2+2H 2O↑
(10)2Ba(HCO 3) 2+BaF 2+3B 2O 3→Ba 3B 6O 11F 2+4CO 2↑+2H 2O↑
(11)2BaC 2O 4+BaF 2+3B 2O 3→Ba 3B 6O 11F 2+2CO 2↑+2CO。
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 barium fluoborate non-linear optic crystal that adopts the method for the invention to obtain is made, at room temperature, make light source with the 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.
Description of drawings
Fig. 1 is Ba of the present invention 3B 6O 11F 2The X-ray diffraction figure of powder.
Fig. 2 is Ba of the present invention 3B 6O 11F 2The 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 Ba 3B 6O 11F 2Crystal, 4 is outgoing beam, 5 is filter plate.
Embodiment
The present invention is described in detail below in conjunction with drawings and Examples:
Embodiment 1:
Press reaction formula: 2BaCO 3+ BaF 2+ 6H 3BO 3→ Ba 3B 6O 11F 2+ 2CO 2↑+9H 2O ↑ synthetic Ba 3B 6O 11F 2Compound:
With BaCO 3, BaF 2, H 3BO 3Took by weighing in 2: 1: 6 in molar ratio and put into mortar, mix and carefully grinding, then pack in the opening corundum crucible of Φ 100mm * 100mm, put into retort furnace, slowly be warming up to 550 ℃, constant temperature 24 hours is cooled to room temperature, taking-up is put into retort furnace after grinding for the second time, be warming up to 650 ℃, constant temperature 24 hours is cooled to room temperature again, taking-up is put into retort furnace after grinding for the third time, be warming up to 780 ℃, constant temperature 48 hours takes out and makes barium fluoborate compound single-phase polycrystal powder through grinding again, this product is carried out X-ray analysis, gained X-ray spectrogram and barium fluoborate Ba 3B 6O 11F 2The X-ray spectrogram that single crystal structure obtains is consistent;
With the barium fluoborate Ba that obtains 3B 6O 11F 2Compound single-phase polycrystal powder and fusing assistant NaF-H 3BO 3Ba in molar ratio 3B 6O 11F 2: NaF-H 3BO 3=1: 3, wherein NaF and H 3BO 3Mol ratio be 3: 4, be mixed, in the opening platinum crucible of the Φ 80mm * 80mm that packs into, be heated to 780 ℃ with the temperature rise rate of 30 ℃/h, constant temperature 15 hours obtains mixed molten liquid, is cooled to 735 ℃ again;
To room temperature, spontaneous crystallization obtains the barium fluoborate seed crystal with the speed slow cooling of 0.5 ℃/h of temperature;
Growing crystal in the compound liquation: with the Ba that obtains 3B 6O 11F 2Seed crystal is fixed on the seed rod seed crystal under the crystal growing furnace top, and preheating seed crystal 10 minutes on the mixed molten liquid surface in the immersed in liquid level, makes seed crystal carry out melt back in mixed molten liquid first, constant temperature 30 minutes, and fast cooling is to 730 ℃ of temperature of saturation;
With 2 ℃/day speed cooling, with the rotating speed rotary seed crystal rod of 10rpm, after the crystal growth finishes, make crystal break away from liquid level again, be down to room temperature with the speed of 10 ℃/hour of temperature, can obtain to be of a size of the Ba of 56mm * 40mm * 30mm 3B 6O 11F 2Crystal.
Raw material barium carbonate in the reaction formula can be replaced with barium oxide or nitrate of baryta or barium oxalate or hydrated barta or barium bicarbonate, and boric acid can be replaced by boron oxide.
Embodiment 2:
Press reaction formula: 2Ba (NO 3) 2+ BaF 2+ 6H 3BO 3→ Ba 3B 6O 11F 2+ 2NO 2↑+9H 2O ↑+3O 2↑ synthetic Ba 3B 6O 11F 2Compound:
With Ba (NO 3) 2, BaF 2, H 3BO 3Directly took by weighing raw material in 2: 1: 6 in molar ratio, with raw material and the fusing assistant Na that takes by weighing 2O-H 3BO 3Be mixed in 1: 4 in molar ratio, wherein Na 2O and H 3BO 3Mol ratio be 2: 5, in the opening platinum crucible of the Φ 80mm * 80mm that packs into, be warming up to 745 ℃ of temperature, constant temperature 60 hours obtains mixed molten liquid, is cooling to 715 ℃ of temperature;
To room temperature, spontaneous crystallization obtains the barium fluoborate seed crystal with the speed slow cooling of 1.5 ℃/h of temperature;
With the Ba that obtains 3B 6O 11F 2Seed crystal is fixed on the seed rod seed crystal under the crystal growing furnace top, and preheating seed crystal 10 minutes on the mixed molten liquid surface under the immersed in liquid level, makes seed crystal carry out melt back in mixed molten liquid first, constant temperature 30 minutes, and fast cooling is to 710 ℃ of temperature of saturation;
Again with the speed slow cooling of 1 ℃/day of temperature, rotary seed crystal rod not is after crystal grows into required yardstick, crystal is lifted from molten surface, be down to room temperature with 20 ℃/h of temperature speed, then crystal taken out from burner hearth, can obtain to be of a size of the Ba of 36mm * 22mm * 15mm 3B 6O 11F 2Crystal.
Raw material nitrate of baryta in the reaction formula can be replaced with barium carbonate or barium oxide or barium oxalate or hydrated barta or barium bicarbonate, and boric acid can be replaced by boron oxide.
Embodiment 3:
Press reaction formula: 2BaO+BaF 2+ 6H 3BO 3→ Ba 3B 6O 11F 2+ 9H 2O ↑ synthetic Ba 3B 6O 11F 2Compound:
With BaO, BaF 2, H 3BO 3Put into mortar in 2: 1: 6 in molar ratio, mix and carefully grinding, in the opening corundum crucible of the Φ 100mm * 100mm that then packs into, with its compression, put into retort furnace, slowly be warming up to 550 ℃, constant temperature 24 hours, take out after cooling crucible, this moment, sample was more loose, then took out sample and again ground evenly, place again crucible, in retort furnace, in 780 ℃ of temperature constant temperature 48 hours again, with its taking-up, put into mortar and smash grinding to pieces and namely get Ba 3B 6O 11F 2Compound carries out X-ray analysis to this product, gained X-ray spectrogram and barium fluoborate Ba 3B 6O 11F 2The X-ray spectrogram that single crystal structure obtains is consistent;
With synthetic Ba 3B 6O 11F 2Compound and fusing assistant LiF-PbO be in molar ratio=1: 5, and wherein the mol ratio of LiF and PbO is to be mixed at 1: 1, in the opening platinum crucible of the Φ 80mm * 80mm that packs into, is warming up to 720 ℃ of temperature, and constant temperature 80 hours obtains mixed molten liquid, is down to 660 ℃ of temperature again;
To room temperature, spontaneous crystallization obtains the barium fluoborate seed crystal with the speed slow cooling of 2.5 ℃/h of temperature;
The seed crystal that obtains is fixed on the seed rod seed crystal under the crystal growing furnace top, first preheating seed crystal 10 minutes on the mixed molten liquid surface under the part immersed in liquid level, makes seed crystal carry out melt back in mixed molten liquid, constant temperature 20 minutes, fast cooling is to 650 ℃ of temperature of saturation;
Again with the speed slow cooling of 2 ℃/day of temperature, with the rotating speed rotary seed crystal rod of 30rpm, after crystal grows into required yardstick, crystal is lifted from molten surface, be down to room temperature with 30 ℃/h of temperature speed, then crystal taken out from burner hearth, can obtain to be of a size of the Ba of 33mm * 30mm * 20mm 3B 6O 11F 2Crystal.
Raw material barium oxide in the reaction formula can be replaced with barium carbonate or nitrate of baryta or barium oxalate or hydrated barta or barium bicarbonate, and boric acid can be replaced by boron oxide.
Embodiment 4:
Press reaction formula: 2Ba (OH) 2+ BaF 2+ 6H 3BO 3→ Ba 3B 6O 11F 2+ 11H 2O ↑ synthetic Ba 3B 6O 11F 2Compound:
With Ba (OH) 2, BaF 2And H 3BO 3Directly took by weighing raw material in 2: 1: 6 in molar ratio, with raw material and the fusing assistant NaF-H that takes by weighing 3BO 3Be mixed in 1: 3 in molar ratio, wherein NaF and H 3BO 3Mol ratio be 1: 1, in the opening platinum crucible of the Φ 80mm * 80mm that packs into, be warming up to 765 ℃ of temperature, constant temperature 10 hours obtains mixed molten liquid, is cooling to 715 ℃ of temperature;
To room temperature, spontaneous crystallization obtains the barium fluoborate seed crystal with the speed slow cooling of 2.5 ℃/h of temperature;
With the Ba that obtains 3B 6O 11F 2Seed crystal is fixed on the seed rod seed crystal under the crystal growing furnace top, and preheating seed crystal 5 minutes on the mixed molten liquid surface under the immersed in liquid level, makes seed crystal carry out melt back in mixed molten liquid first, constant temperature 5 minutes, and fast cooling is to 700 ℃ of temperature of saturation;
Then with the speed slow cooling of 2 ℃/day of temperature, with the rotating speed rotary seed crystal rod of 50rpm, after crystal grows into required yardstick, crystal is lifted from molten surface, be down to room temperature with temperature 60 C/h speed, then crystal taken out from burner hearth, can obtain to be of a size of the Ba of 30mm * 28mm * 15mm 3B 6O 11F 2Crystal.
Feed hydrogen barium oxide in the reaction formula can be replaced with barium carbonate or nitrate of baryta or barium oxalate or barium oxide or barium bicarbonate, and boric acid can be replaced by boron oxide.
Embodiment 5:
Press reaction formula: 2Ba (HCO 3) 2+ BaF 2+ 6H 3BO 3→ Ba 3B 6O 11F 2+ 4CO 2↑+11H 2O ↑ synthetic Ba (HCO 3) 2Compound:
With Ba (HCO 3) 2, BaF 2, H 3BO 3Directly took by weighing raw material in 2: 1: 6 in molar ratio, with the raw material that takes by weighing and fusing assistant NaF-PbO 1: 6 in molar ratio, be mixed, wherein NaF and PbO mol ratio are 3: 1, pack in the opening platinum crucible of Φ 80mm * 80mm, be warming up to 680 ℃ of temperature, constant temperature 60 hours, obtain mixed molten liquid, be down to again 620 ℃ of temperature;
To room temperature, spontaneous crystallization obtains the barium fluoborate seed crystal with the speed slow cooling of 3.5 ℃/h of temperature;
With the Ba that obtains 3B 6O 11F 2Seed crystal is fixed on the seed rod seed crystal under the crystal growing furnace top, and preheating seed crystal 15 minutes on the mixed molten liquid surface under the immersed in liquid level, makes seed crystal carry out melt back in mixed molten liquid first, 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 from molten surface, be down to room temperature with 1 ℃/h of temperature speed, then crystal taken out from burner hearth, can obtain to be of a size of the Ba of 25mm * 24mm * 10mm 3B 6O 11F 2Crystal.
Raw material barium bicarbonate in the reaction formula can be replaced with barium carbonate or nitrate of baryta or barium oxalate or hydrated barta or barium oxide, and boric acid can be replaced by boron oxide.
Embodiment 6:
Press reaction formula: 2BaCO 3+ BaF 2+ 3B 2O 3→ Ba 3B 6O 11F 2+ 2CO 2↑ synthetic Ba 3B 6O 11F 2Compound:
With BaCO 3, BaF 2, B 2O 3Directly took by weighing raw material in 2: 1: 3 in molar ratio, with raw material and the fusing assistant H that takes by weighing 3BO 3-PbO was mixed in 1: 6 in molar ratio, wherein H 3BO 3With the PbO mol ratio be 3: 1, in the opening platinum crucible of the Φ 80mm * 80mm that packs into, be warming up to 650 ℃ of temperature, constant temperature 80 hours obtains mixed molten liquid, is down to 615 ℃ of temperature again;
To room temperature, spontaneous crystallization obtains the barium fluoborate seed crystal with the speed slow cooling of 5 ℃/h of temperature;
With the Ba that obtains 3B 6O 11F 2Seed crystal is fixed on the seed rod seed crystal under the crystal growing furnace top, and preheating seed crystal 20 minutes on the mixed molten liquid surface under the immersed in liquid level, makes seed crystal carry out melt back in mixed molten liquid first, constant temperature 5 minutes, and fast cooling is to 610 ℃ 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, with the crystal body from molten surface, be down to room temperature with 15 ℃/h of temperature speed, then crystal taken out from burner hearth, can obtain to be of a size of the Ba of 35mm * 25mm * 20mm 3B 6O 11F 2Crystal.
Raw material barium oxide in the reaction formula can be replaced with barium carbonate or nitrate of baryta or barium oxalate or hydrated barta or barium bicarbonate, and boron oxide can be replaced by boric acid.
Embodiment 7
Press reaction formula: 2Ba (NO 3) 2+ BaF 2+ 3B 2O 3→ Ba 3B 6O 11F 2+ 4NO 2↑+O 2↑ synthetic Ba 3B 6O 11F 2Compound;
With Ba (NO 3) 2, BaF 2, B 2O 3Directly took by weighing raw material in 2: 1: 3 in molar ratio, the raw material and the fusing assistant NaF-PbO that take by weighing were mixed in 1: 2 in molar ratio, wherein NaF and PbO mol ratio are in the opening platinum crucible of 3: 2 Φ 80mm * 80mm that pack into, be warming up to 760 ℃ of temperature, constant temperature 80 hours, obtain mixed molten liquid, be down to again 710 ℃ of temperature;
To room temperature, spontaneous crystallization obtains the barium fluoborate seed crystal with the speed slow cooling of 10 ℃/h of temperature;
The seed crystal that obtains is fixed on the seed rod seed crystal under the crystal growing furnace top, first preheating seed crystal 25 minutes on the mixed molten liquid surface under the part immersed in liquid level, makes seed crystal carry out melt back in mixed molten liquid, constant temperature 25 minutes, fast cooling is to 700 ℃ of temperature of saturation;
Lower the temperature with the speed of 5 ℃/day of temperature again, with the rotating speed rotary seed crystal rod of 30rpm, after crystal grows into required yardstick, crystal is lifted from molten surface, be down to room temperature with 35 ℃/h of temperature speed, then crystal taken out from burner hearth, can obtain to be of a size of the Ba of 22mm * 32mm * 20mm 3B 6O 11F 2Crystal.
Raw material nitrate of baryta in the reaction formula can be replaced with barium bicarbonate or barium carbonate or barium oxalate or hydrated barta or barium oxide, and boron oxide can be replaced by boric acid.
Embodiment 8
Press reaction formula: 2BaO+BaF 2+ 3B 2O 3→ Ba 3B 6O 11F 2Synthetic Ba 3B 6O 11F 2Compound;
With BaO, BaF 2, B 2O 3Put into mortar in 2: 1: 3 in molar ratio, mix and carefully grinding, in the opening corundum crucible of the Φ 100mm * 100mm that then packs into, with its compression, put into retort furnace, slowly be warming up to 550 ℃ of temperature, constant temperature 24 hours, take out after cooling crucible, this moment, sample was more loose, then took out sample and again ground evenly, place again crucible, in retort furnace, in 780 ℃ of temperature constant temperature 48 hours again, with its taking-up, put into mortar and smash grinding to pieces and namely get Ba 3B 6O 11F 2Compound carries out X-ray analysis to this product, gained X-ray spectrogram and barium fluoborate Ba 3B 6O 11F 2The X-ray spectrogram that single crystal structure obtains is consistent;
Then with synthetic Ba 3B 6O 11F 2Compound and fusing assistant Na 2O-PbO 1: 4 in molar ratio is mixed, wherein Na 2O and PbO mol ratio are 2: 2, in the opening platinum crucible of the Φ 80mm * 80mm that packs into, are warming up to 770 ℃ of temperature, and constant temperature 70 hours obtains mixed molten liquid, is down to 725 ℃ of temperature again;
To room temperature, spontaneous crystallization obtains the barium fluoborate seed crystal with the speed slow cooling of 4.0 ℃/h of temperature;
With the Ba that obtains 3B 6O 11F 2Seed crystal is fixed on the seed rod seed crystal under the crystal growing furnace top, and preheating seed crystal 8 minutes on the mixed molten liquid surface under the immersed in liquid level, makes seed crystal carry out melt back in mixed molten liquid first, constant temperature 8 minutes, and fast cooling is to 720 ℃ of temperature of saturation;
Again with the speed slow cooling of 0.8 ℃/day of temperature, rotating speed rotation seed crystal crucible with 10rpm, after crystal grows into required yardstick, with the crystal body from molten surface, be down to room temperature with 5 ℃/h of temperature speed, then crystal is taken out from burner hearth, can obtain to be of a size of the Ba of 18mm * 22mm * 15mm 3B 6O 11F 2Crystal.
Raw material barium oxide in the reaction formula can be replaced with barium carbonate or barium bicarbonate or barium oxalate or hydrated barta or nitrate of baryta, and boron oxide can be replaced by boric acid.
Embodiment 9
Press reaction formula: 2Ba (OH) 2+ BaF 2+ 3B 2O 3→ Ba 3B 6O 11F 2+ 2H 2O ↑ synthetic Ba 3B 6O 11F 2Compound:
With Ba (OH) 2, BaF 2, B 2O 3Put into mortar in 2: 1: 3 in molar ratio, mix and carefully grinding, in the opening corundum crucible of the Φ 100mm * 100mm that then packs into, with its compression, put into retort furnace, slowly be warming up to 550 ℃ of temperature, constant temperature 24 hours, take out after cooling crucible, this moment, sample was more loose, then took out sample and again ground evenly, place again crucible, in retort furnace, in 780 ℃ of temperature constant temperature 48 hours again, with its taking-up, put into mortar and smash grinding to pieces and namely get Ba 3B 6O 11F 2Compound carries out X-ray analysis to this product, gained X-ray spectrogram and barium fluoborate Ba 3B 6O 11F 2The X-ray spectrogram that single crystal structure obtains is consistent;
Then with synthetic Ba 3B 6O 11F 2Compound and fusing assistant H 3BO 3-PbO 1: 4 in molar ratio is mixed H 3BO and PbO mol ratio are 2: 1, in the opening platinum crucible of the Φ 80mm * 80mm that packs into, are warming up to 630 ℃ of temperature, and constant temperature 45 hours obtains mixed molten liquid, is down to 620 ℃ of temperature again;
To room temperature, spontaneous crystallization obtains the barium fluoborate seed crystal with the speed slow cooling of 6.5 ℃/h of temperature;
With the Ba that obtains 3B 6O 11F 2Seed crystal is fixed on the seed rod seed crystal under the crystal growing furnace top, and preheating seed crystal 15 minutes on the mixed molten liquid surface under the immersed in liquid level, makes seed crystal carry out melt back in mixed molten liquid first, constant temperature 15 minutes, and fast cooling is to 615 ℃ of temperature of saturation;
Again with the speed slow cooling of 2 ℃/day of temperature, with the rotating speed rotary seed crystal rod of 60rpm, after crystal grows into required yardstick, with the crystal body from molten surface, be down to room temperature with 80 ℃/h of temperature speed, then crystal taken out from burner hearth, can obtain to be of a size of the Ba of 24mm * 22mm * 15mm 3B 6O 11F 2Crystal.
Feed hydrogen barium oxide in the reaction formula can be replaced with barium carbonate or barium bicarbonate or barium oxalate or nitrate of baryta or barium oxide, and boron oxide can be replaced by boric acid.
Embodiment 10
Press reaction formula: 2Ba (HCO 3) 2+ BaF 2+ 3B 2O 3→ Ba 3B 6O 11F 2+ 4CO 2↑+2H 2O ↑ synthetic Ba 3B 6O 11F 2Compound:
With Ba (HCO 3) 2, BaF 2, B 2O 3Put into mortar in 2: 1: 3 in molar ratio, mix and carefully grinding, in the opening corundum crucible of the Φ 100mm * 100mm that then packs into, with its compression, put into retort furnace, slowly be warming up to 550 ℃ of temperature, constant temperature 24 hours, take out after cooling crucible, this moment, sample was more loose, then took out sample and again ground evenly, place again crucible, in retort furnace, in 780 ℃ of temperature constant temperature 48 hours again, with its taking-up, put into mortar and smash grinding to pieces and namely get Ba 3B 6O 11F 2Compound carries out X-ray analysis to this product, gained X-ray spectrogram and barium fluoborate Ba 3B 6O 11F 2The X-ray spectrogram that single crystal structure obtains is consistent; ,
With synthetic Ba 3B 6O 11F 2Compound and fusing assistant NaF-PbO were mixed in 3: 2 in molar ratio, and wherein NaF and PbO mol ratio are 2: 1, in the opening platinum crucible of the Φ 80mm * 80mm that packs into, were warming up to 900 ℃ of temperature, and constant temperature obtained mixed molten liquid in 5 hours, was down to 750 ℃ of temperature again;
To room temperature, spontaneous crystallization obtains the barium fluoborate seed crystal with the speed slow cooling of 4.0 ℃/h of temperature;
With the Ba that obtains 3B 6O 11F 2Seed crystal is fixed on the seed rod seed crystal under the crystal growing furnace top, and preheating seed crystal 20 minutes on the mixed molten liquid surface under the immersed in liquid level, makes seed crystal carry out melt back in mixed molten liquid first, constant temperature 25 minutes, and fast cooling is to 745 ℃ of temperature of saturation;
Then lower the temperature with the speed of 3 ℃/day of temperature, with the rotating speed rotary seed crystal rod of 50rpm, after crystal grows into required yardstick, with the crystal body from molten surface, be down to room temperature with temperature 70 C/h speed, then crystal taken out from burner hearth, can obtain to be of a size of the Ba of 22mm * 21mm * 16mm 3B 6O 11F 2Crystal.
Raw material barium bicarbonate in the reaction formula can be replaced with barium carbonate or hydrated barta or barium oxalate or nitrate of baryta or barium oxide, and boron oxide can be replaced by boric acid;
Embodiment 11
Press reaction formula: 2BaC 2O 4+ BaF 2+ 3B 2O 3→ Ba 3B 6O 11F 2+ 2CO 2↑+2CO synthesizes Ba 3B 6O 11F 2Compound:
With BaC 2O 4, BaF 2, B 2O 3Put into mortar in 2: 1: 3 in molar ratio, mix and carefully grinding, in the opening corundum crucible of the Φ 100mm * 100mm that then packs into, with its compression, put into retort furnace, slowly be warming up to 550 ℃ of temperature, constant temperature 24 hours, take out after cooling crucible, this moment, sample was more loose, then took out sample and again ground evenly, place again crucible, in retort furnace, in 780 ℃ of temperature constant temperature 48 hours again, with its taking-up, put into mortar and smash grinding to pieces and namely get Ba 3B 6O 11F 2Compound carries out X-ray analysis to this product, gained X-ray spectrogram and barium fluoborate Ba 3B 6O 11F 2The X-ray spectrogram that single crystal structure obtains is consistent; ,
With synthetic Ba 3B 6O 11F 2Compound and fusing assistant H 3BO 3-PbO was mixed in 1: 3 in molar ratio, wherein H 3BO 3With the PbO mol ratio be 5: 1, in the opening platinum crucible of the Φ 80mm * 80mm that packs into, be warming up to 800 ℃ of temperature, constant temperature obtained mixed molten liquid in 50 hours, was down to 720 ℃ of temperature again;
To room temperature, spontaneous crystallization obtains the barium fluoborate seed crystal with the speed slow cooling of 4.0 ℃/h of temperature;
With the Ba that obtains 3B 6O 11F 2Seed crystal is fixed on the seed rod seed crystal under the crystal growing furnace top, and preheating seed crystal 20 minutes on the mixed molten liquid surface under the immersed in liquid level, makes seed crystal carry out melt back in mixed molten liquid first, and constant temperature 25 minutes is cooled to 715 ℃ of temperature of saturation;
Then lower the temperature with the speed of 2 ℃/day of temperature, with the rotating speed rotary seed crystal rod of 28rpm, after crystal grows into required yardstick, with the crystal body from molten surface, be down to room temperature with 25 ℃/h of temperature speed, then crystal taken out from burner hearth, can obtain to be of a size of the Ba of 30mm * 22mm * 15mm 3B 6O 11F 2Crystal.
Raw material barium oxalate in the reaction formula can be replaced with barium carbonate or hydrated barta or barium bicarbonate or nitrate of baryta or barium oxide, and boron oxide can be replaced by boric acid;
Embodiment 12
With embodiment 1-11 gained Ba arbitrarily 3B 6O 11F 2Crystal is by the frequency doubling device of the size 5mm * 5mm * 6mm of direction processing that is complementary, by being placed in shown in the accompanying drawing 2 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 Ba by transferring QNd:YAG laser apparatus 1 to send wavelength 3B 6O 11F 2Monocrystalline 3, producing wavelength is the green frequency doubled light of 532nm, and output intensity is 5 times of equal conditions KDP, and 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. compound barium fluoborate, the chemical formula that it is characterized in that this compound is Ba 3B 6O 11F 2, molecular weight 690.88 adopts the solid reaction process synthetic compound.
2. barium fluoborate non-linear optic crystal, the chemical formula that it is characterized in that this crystal is Ba 3B 6O 11F 2, do not have symmetry centre, belong to oblique system, spacer P2 (1), unit cell parameters is
Figure FSA00000567065000011
Figure FSA00000567065000012
Figure FSA00000567065000013
Figure FSA00000567065000014
β=101.351 (4) ° .Z=2,
Figure FSA00000567065000015
Molecular weight 690.88.
3. the preparation method of compound barium fluoborate non-linear optic crystal according to claim 2 is characterized in that adopting solid reaction process synthetic compound and high temperature solution method growth barium fluoborate non-linear optic crystal, and concrete operations follow these steps to carry out:
A, barium fluoborate compound single-phase polycrystal powder is evenly mixed with fusing assistant, temperature rise rate with temperature 1-30 ℃/h is heated to temperature 650-900 ℃, constant temperature 5-80 hour, obtain mixed molten liquid, be cooled to temperature 610-830 ℃, wherein the mol ratio of barium fluoborate compound single-phase polycrystal powder and fusing assistant is 1: 1-6 again;
Or directly containing barium compound, barium fluoride and boric acid and fusing assistant are mixed, temperature rise rate with temperature 1-30 ℃/h is heated to temperature 650-900 ℃, constant temperature 5-80 hour, obtain mixed molten liquid, be cooled to temperature 610-830 ℃, wherein the mol ratio of containing barium compound, barium fluoride and boric acid and fusing assistant is 2: 1: 6: 1-6 again;
B, preparation barium fluoborate seed crystal: the mixed molten liquid that step a obtains slowly is down to room temperature with the speed of temperature 0.5-10 ℃/h, and spontaneous crystallization obtains the barium fluoborate seed crystal;
C, the crucible that will fill the mixed molten liquid that step a makes are inserted in the crystal growing furnace, the seed crystal that step b is obtained is fixed on the seed rod, seed crystal under the crystal growing furnace top, elder generation's 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, be down to temperature of saturation with the speed of temperature 1-60 ℃/h.
D, again with temperature 0.1-5 ℃/day speed slow cooling, carry out the growth of crystal with 0-60rpm rotating speed rotary seed crystal rod, after required yardstick is arrived in single crystal growing, crystal is lifted from the 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 the barium fluoborate non-linear optic crystal.
4. described method according to claim 3 is characterized in that the described containing barium compound of step a is barium carbonate, nitrate of baryta, barium oxide, hydrated barta, barium bicarbonate or barium oxalate.
5. described method according to claim 4 is characterized in that the described fusing assistant of step a is NaF-H 3BO 3, H 3BO 3-Na 2O, Na 2O-PbO, LiF-PbO, NaF-PbO or H 3BO 3-PbO.
6. described method according to claim 5 is characterized in that fusing assistant NaF-H 3BO 3NaF and H in the system 3BO 3Mol ratio be 1-5: 3-6; The mol ratio of fluorochemical and plumbous oxide is 1-5: 1-6 in LiF-PbO or the NaF-PbO system; H 3BO 3-PbO or H 3BO 3-Na 2The mol ratio of O system mesoboric acid and oxide compound is 2-5: 1-5; Na 2The mol ratio of sodium oxide and plumbous oxide is 1-5: 0.1-6 in the O-PbO system.
7. the purposes of barium fluoborate non-linear optic crystal according to claim 2 is characterized in that, for the preparation of frequency multiplication producer, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
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