CN102978702B - 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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CN102978702B
CN102978702B CN201110258171.0A CN201110258171A CN102978702B CN 102978702 B CN102978702 B CN 102978702B CN 201110258171 A CN201110258171 A CN 201110258171A CN 102978702 B CN102978702 B CN 102978702B
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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 Beta=101.351 (4) deg., 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 utilizing this crystal to make.
Background technology
Current predominant non-linearity 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 there is obvious weak point: deliquescence as easy in crystal, growth cycle are long, layer growth habit is serious and expensive.Therefore, find new non-linear optical crystal material and remain an extremely important and large order.
Thus in recent years, when Development of Novel non-linear optic crystal, not only focus on 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 is easily prepared, the non-linear optic crystal of cheap large-size high-quality can be obtained.Introduce under alkaline earth metal cation and halide-ions instruct with the design philosophy improving its performance in boron oxygen framework, negatively charged ion is based on boron oxygen functional motif, and its band gap is comparatively large, and two-photon absorption probability is little; Laser damage threshold is higher; Be beneficial to the non-linear optical effect that acquisition is stronger; B-O key is beneficial to wide band light transmission.Cation selective alkaline-earth metal ions, its in ultraviolet region without d 0the transition of electronics, is conducive to UV-permeable, and its transparency range has been widened in the introducing of halide-ions simultaneously.
Summary of the invention
The object of the invention is to provide a kind of compound barium fluoborate, and barium fluoborate non-linear optic crystal, and chemical formula is Ba 3b 6o 11f 2.
Another object of the present invention is to provide the preparation method adopting solid reaction process synthetic compound and high temperature solution method growth barium fluoborate non-linear optic crystal.
Further object of the present invention is to provide a kind of purposes of barium fluoborate device for non-linear optical, for the preparation of doubly frequency generator, 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 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 β=101.351 (4) ° .Z=2, its powder SHG effect reaches KDP (KH 2pO 4) 3 times.
The preparation method of described barium fluoborate non-linear optic crystal, adopt solid reaction process synthetic compound and high temperature solution method growth barium fluoborate non-linear optic crystal, concrete operations follow these steps to carry out:
A, by barium fluoborate compound single-phase polycrystal powder and fusing assistant Homogeneous phase mixing, temperature 650-900 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 610-830 DEG C again, wherein the mol ratio of barium fluoborate compound single-phase polycrystal powder and fusing assistant is 1: 1-6;
Or directly containing barium compound, barium fluoride and boric acid are mixed with fusing assistant, temperature 650-900 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 610-830 DEG C again, wherein the mol ratio of containing barium compound, barium fluoride and boric acid and fusing assistant is 2: 1: 6: 1-6;
B, prepare barium fluoborate 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 barium fluoborate 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, barium fluoborate non-linear optic crystal can be obtained.
Containing barium compound described in step a is barium carbonate, nitrate of baryta, barium oxide, hydrated barta, barium bicarbonate or barium oxalate.
Fusing assistant described in 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 system 3bO 3mol ratio be 1-5: 3-6; In LiF-PbO or NaF-PbO system, the mol ratio of fluorochemical and plumbous oxide is 1-5: 1-6; 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 2in O-PbO system, the mol ratio of sodium oxide and plumbous oxide is 1-5: 0.1-6.
The purposes of described barium fluoborate non-linear optic crystal, for the preparation of doubly frequency generator, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
Barium fluoborate compound provided by the invention, its chemical formula is Ba 3b 6o 11f 2; It adopts solid reaction process to prepare 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。
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 compound barium fluoborate 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 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 makes, wherein 1 is laser apparatus, and 2 for sending light beam, and 3 is Ba 3b 6o 11f 2crystal, 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: 2BaCO 3+ BaF 2+ 6H 3bO 3→ Ba 3b 6o 11f 2+ 2CO 2↑+9H 2o ↑ synthesis Ba 3b 6o 11f 2compound:
By BaCO 3, BaF 2, H 3bO 3take put into mortar at 2: 1: 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 550 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 650 DEG C again, constant temperature 24 hours, be cooled to room temperature, take out and put into retort furnace after third time grinding, be warming up to 780 DEG C again, constant temperature 48 hours, take out through grinding obtained barium fluoborate compound single-phase polycrystal powder, X-ray analysis is carried out 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,
By the barium fluoborate Ba obtained 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, carry out mixture, load in the opening platinum crucible of Φ 80mm × 80mm, be heated to 780 DEG C with the temperature rise rate of 30 DEG C/h, constant temperature 15 hours, obtains mixed molten liquid, then is cooled to 735 DEG C;
With the speed slow cooling of temperature 0.5 DEG C/h to room temperature, spontaneous crystallization obtains barium fluoborate seed crystal;
Growing crystal in compound liquation: by the Ba obtained 3b 6o 11f 2seed 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 730 DEG C;
Again with the speed of 2 DEG C of/day cooling, 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 Ba being of a size of 56mm × 40mm × 30mm can be obtained 3b 6o 11f 2crystal.
Oxide spinel barium in 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:
By reaction formula: 2Ba (NO 3) 2+ BaF 2+ 6H 3bO 3→ Ba 3b 6o 11f 2+ 2NO 2↑+9H 2o ↑+3O 2↑ synthesis Ba 3b 6o 11f 2compound:
By Ba (NO 3) 2, BaF 2, H 3bO 3directly take raw material at 2: 1: 6 in molar ratio, by the raw material that takes and fusing assistant Na 2o-H 3bO 3carry out mixture at 1: 4 in molar ratio, wherein Na 2o and H 3bO 3mol ratio be 2: 5, load in the opening platinum crucible of Φ 80mm × 80mm, be warming up to temperature 745 DEG C, constant temperature 60 hours, obtains mixed molten liquid, is cooling to temperature 715 DEG C;
With the speed slow cooling of temperature 1.5 DEG C/h to room temperature, spontaneous crystallization obtains barium fluoborate seed crystal;
By the Ba obtained 3b 6o 11f 2seed 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 710 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 Ba being of a size of 36mm × 22mm × 15mm can be obtained 3b 6o 11f 2crystal.
Raw material nitrate of baryta in 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:
By reaction formula: 2BaO+BaF 2+ 6H 3bO 3→ Ba 3b 6o 11f 2+ 9H 2o ↑ synthesis Ba 3b 6o 11f 2compound:
By BaO, BaF 2, H 3bO 3put into mortar at 2: 1: 6 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 550 DEG C, constant temperature 24 hours, take out crucible after cooling, now sample is more loose, then takes out sample and again grinds evenly, be placed in crucible again, in temperature 780 DEG C constant temperature 48 hours again in retort furnace, taken out, put into mortar and smash grinding to pieces and namely obtain 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;
By the Ba of synthesis 3b 6o 11f 2compound and fusing assistant LiF-PbO are in molar ratio=1: 5, and wherein the mol ratio of LiF and PbO is carry out mixture at 1: 1, and load in the opening platinum crucible of Φ 80mm × 80mm, be warming up to temperature 720 DEG C, constant temperature 80 hours, obtains mixed molten liquid, then is down to temperature 660 DEG C;
With the speed slow cooling of temperature 2.5 DEG C/h to room temperature, spontaneous crystallization obtains barium fluoborate 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 10 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 20 minutes, fast cooling is to temperature of saturation 650 DEG C;
Again with the speed slow cooling of temperature 2 DEG C/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 30 DEG C/h speed, then crystal taken out from burner hearth, the Ba being of a size of 33mm × 30mm × 20mm can be obtained 3b 6o 11f 2crystal.
Material oxidation barium in 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:
By reaction formula: 2Ba (OH) 2+ BaF 2+ 6H 3bO 3→ Ba 3b 6o 11f 2+ 11H 2o ↑ synthesis Ba 3b 6o 11f 2compound:
By Ba (OH) 2, BaF 2and H 3bO 3directly take raw material at 2: 1: 6 in molar ratio, by the raw material that takes and fusing assistant NaF-H 3bO 3carry out mixture at 1: 3 in molar ratio, wherein NaF and H 3bO 3mol ratio be 1: 1, load in the opening platinum crucible of Φ 80mm × 80mm, be warming up to temperature 765 DEG C, constant temperature 10 hours, obtains mixed molten liquid, is cooling to temperature 715 DEG C;
With the speed slow cooling of temperature 2.5 DEG C/h to room temperature, spontaneous crystallization obtains barium fluoborate seed crystal;
By the Ba obtained 3b 6o 11f 2seed crystal is fixed on from seed crystal crystal growing furnace top on seed rod, and first at mixed molten liquid preheating seed crystal 5 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 700 DEG C;
Then with the speed slow cooling of temperature 2 DEG C/day, with the rotating speed rotary seed crystal rod of 50rpm, arrive after required yardstick until crystal growth, by crystal lift-off molten surface, be down to room temperature with temperature 60 C/h speed, then crystal taken out from burner hearth, the Ba being of a size of 30mm × 28mm × 15mm can be obtained 3b 6o 11f 2crystal.
Feed hydrogen barium oxide in 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:
By reaction formula: 2Ba (HCO 3) 2+ BaF 2+ 6H 3bO 3→ Ba 3b 6o 11f 2+ 4CO 2↑+11H 2o ↑ synthesis Ba (HCO 3) 2compound:
By Ba (HCO 3) 2, BaF 2, H 3bO 3directly take raw material at 2: 1: 6 in molar ratio, by the raw material that takes and fusing assistant NaF-PbO in molar ratio 1: 6, carry out mixture, wherein NaF and PbO mol ratio is 3: 1, load in the opening platinum crucible of Φ 80mm × 80mm, be warming up to temperature 680 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 barium fluoborate seed crystal;
By the Ba obtained 3b 6o 11f 2seed 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 Ba being of a size of 25mm × 24mm × 10mm can be obtained 3b 6o 11f 2crystal.
Oxide spinel hydrogen barium in 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:
By reaction formula: 2BaCO 3+ BaF 2+ 3B 2o 3→ Ba 3b 6o 11f 2+ 2CO 2↑ synthesis Ba 3b 6o 11f 2compound:
By BaCO 3, BaF 2, B 2o 3directly take raw material at 2: 1: 3 in molar ratio, by the raw material that takes and fusing assistant H 3bO 3-PbO carries out mixture, wherein H in molar ratio at 1: 6 3bO 3be 3: 1 with PbO mol ratio, load in the opening platinum crucible of Φ 80mm × 80mm, be warming up to temperature 650 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 barium fluoborate seed crystal;
By the Ba obtained 3b 6o 11f 2seed 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 610 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 Ba being of a size of 35mm × 25mm × 20mm can be obtained 3b 6o 11f 2crystal.
Material oxidation barium in 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
By reaction formula: 2Ba (NO 3) 2+ BaF 2+ 3B 2o 3→ Ba 3b 6o 11f 2+ 4NO 2↑+O 2↑ synthesis Ba 3b 6o 11f 2compound;
By Ba (NO 3) 2, BaF 2, B 2o 3directly take raw material at 2: 1: 3 in molar ratio, the raw material taken and fusing assistant NaF-PbO are carried out mixture in molar ratio at 1: 2, wherein NaF and PbO mol ratio is in the opening platinum crucible of 3: 2 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 710 DEG C;
With the speed slow cooling of temperature 10 DEG C/h to room temperature, spontaneous crystallization obtains barium fluoborate 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 700 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 Ba being of a size of 22mm × 32mm × 20mm can be obtained 3b 6o 11f 2crystal.
Raw material nitrate of baryta in 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
By reaction formula: 2BaO+BaF 2+ 3B 2o 3→ Ba 3b 6o 11f 2synthesis Ba 3b 6o 11f 2compound;
By BaO, BaF 2, B 2o 3put into mortar at 2: 1: 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 550 DEG C, constant temperature 24 hours, take out crucible after cooling, now sample is more loose, then takes out sample and again grinds evenly, be placed in crucible again, in temperature 780 DEG C constant temperature 48 hours again in retort furnace, taken out, put into mortar and smash grinding to pieces and namely obtain 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 by the Ba of synthesis 3b 6o 11f 2compound and fusing assistant Na 2o-PbO in molar ratio 1: 4, carries out mixture, wherein Na 2o and PbO mol ratio is 2: 2, and load in the opening platinum crucible of Φ 80mm × 80mm, be warming up to temperature 770 DEG C, constant temperature 70 hours, obtains mixed molten liquid, then is down to temperature 725 DEG C;
With the speed slow cooling of temperature 4.0 DEG C/h to room temperature, spontaneous crystallization obtains barium fluoborate seed crystal;
By the Ba obtained 3b 6o 11f 2seed crystal is fixed on from seed crystal crystal growing furnace top on seed rod, and first at mixed molten liquid preheating seed crystal 8 minutes on the surface, under immersed in liquid level, make seed crystal carry out melt back in mixed molten liquid, constant temperature 8 minutes, fast cooling is to temperature of saturation 720 DEG C;
Again with the speed slow cooling of temperature 0.8 DEG C/day, seed crystal crucible is rotated with the rotating speed of 10rpm, arrive after required yardstick until crystal growth, by crystals from molten surface, room temperature is down to temperature 5 DEG C/h speed, then crystal is taken out from burner hearth, the Ba being of a size of 18mm × 22mm × 15mm can be obtained 3b 6o 11f 2crystal.
Material oxidation barium in 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
By reaction formula: 2Ba (OH) 2+ BaF 2+ 3B 2o 3→ Ba 3b 6o 11f 2+ 2H 2o ↑ synthesis Ba 3b 6o 11f 2compound:
By Ba (OH) 2, BaF 2, B 2o 3put into mortar at 2: 1: 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 550 DEG C, constant temperature 24 hours, take out crucible after cooling, now sample is more loose, then takes out sample and again grinds evenly, be placed in crucible again, in temperature 780 DEG C constant temperature 48 hours again in retort furnace, taken out, put into mortar and smash grinding to pieces and namely obtain 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 by the Ba of synthesis 3b 6o 11f 2compound and fusing assistant H 3bO 3-PbO in molar ratio 1: 4, carries out mixture, H 3bO and PbO mol ratio is 2: 1, and load in the opening platinum crucible of Φ 80mm × 80mm, be warming up to temperature 630 DEG C, constant temperature 45 hours, obtains mixed molten liquid, then is down to temperature 620 DEG C;
With the speed slow cooling of temperature 6.5 DEG C/h to room temperature, spontaneous crystallization obtains barium fluoborate seed crystal;
By the Ba obtained 3b 6o 11f 2seed 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 15 minutes, fast cooling is to temperature of saturation 615 DEG C;
Again with the speed slow cooling of temperature 2 DEG C/day, with the rotating speed rotary seed crystal rod of 60rpm, arrive after required yardstick until crystal growth, by crystals from molten surface, be down to room temperature with temperature 80 DEG C/h speed, then crystal taken out from burner hearth, the Ba being of a size of 24mm × 22mm × 15mm can be obtained 3b 6o 11f 2crystal.
Feed hydrogen barium oxide in 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
By reaction formula: 2Ba (HCO 3) 2+ BaF 2+ 3B 2o 3→ Ba 3b 6o 11f 2+ 4CO 2↑+2H 2o ↑ synthesis Ba 3b 6o 11f 2compound:
By Ba (HCO 3) 2, BaF 2, B 2o 3put into mortar at 2: 1: 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 550 DEG C, constant temperature 24 hours, take out crucible after cooling, now sample is more loose, then takes out sample and again grinds evenly, be placed in crucible again, in temperature 780 DEG C constant temperature 48 hours again in retort furnace, taken out, put into mortar and smash grinding to pieces and namely obtain 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; ,
By the Ba of synthesis 3b 6o 11f 2compound and fusing assistant NaF-PbO carry out mixture in molar ratio at 3: 2, and wherein NaF and PbO mol ratio is 2: 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 5 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 barium fluoborate seed crystal;
By the Ba obtained 3b 6o 11f 2seed 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 745 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 Ba being of a size of 22mm × 21mm × 16mm can be obtained 3b 6o 11f 2crystal.
Oxide spinel hydrogen barium in 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
By reaction formula: 2BaC 2o 4+ BaF 2+ 3B 2o 3→ Ba 3b 6o 11f 2+ 2CO 2↑+2CO synthesizes Ba 3b 6o 11f 2compound:
By BaC 2o 4, BaF 2, B 2o 3put into mortar at 2: 1: 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 550 DEG C, constant temperature 24 hours, take out crucible after cooling, now sample is more loose, then takes out sample and again grinds evenly, be placed in crucible again, in temperature 780 DEG C constant temperature 48 hours again in retort furnace, taken out, put into mortar and smash grinding to pieces and namely obtain 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; ,
By the Ba of synthesis 3b 6o 11f 2compound and fusing assistant H 3bO 3-PbO carries out mixture, wherein H in molar ratio at 1: 3 3bO 3be 5: 1 with PbO mol ratio, 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 50 hours, then is down to temperature 720 DEG C;
With the speed slow cooling of temperature 4.0 DEG C/h to room temperature, spontaneous crystallization obtains barium fluoborate seed crystal;
By the Ba obtained 3b 6o 11f 2seed 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 Ba being of a size of 30mm × 22mm × 15mm can be obtained 3b 6o 11f 2crystal.
Raw material barium oxalate in 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
By arbitrary for embodiment 1-11 gained Ba 3b 6o 11f 2crystal 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 Q Nd:YAG laser light source, incident wavelength is 1064nm, and sending wavelength by adjusting QNd:YAG laser apparatus 1 is that Ba injected by the infrared beam 2 of 1064nm 3b 6o 11f 2monocrystalline 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 (4)

1. a compound barium fluoborate non-linear optic crystal, is characterized in that the chemical formula of this crystal is Ba 3b 6o 11f 2, do not have symmetry centre, belong to oblique system, spacer P2 (1), unit cell parameters is β=101.351 (4) °, Z=2, molecular weight 690.88.
2. the preparation method of compound barium fluoborate non-linear optic crystal according to claim 1, it is characterized in that adopting solid reaction process synthetic compound and high temperature solution method growth barium fluoborate non-linear optic crystal, concrete operations follow these steps to carry out:
A, by barium fluoborate compound single-phase polycrystal powder and fusing assistant Homogeneous phase mixing, temperature 650-900 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 610-830 DEG C again, wherein the mol ratio of barium fluoborate compound single-phase polycrystal powder and fusing assistant is 1: 1-6, and described fusing assistant is NaF-H 3bO 3, H 3bO 3-Na 2o, Na 2o-PbO, LiF-PbO, NaF-PbO or H 3bO 3-PbO;
Or be directly barium carbonate, nitrate of baryta, barium oxide, hydrated barta, barium bicarbonate or barium oxalate by containing barium compound, barium fluoride and boric acid and fusing assistant are NaF-H 3bO 3, H 3bO 3-Na 2o, Na 2o-PbO, LiF-PbO, NaF-PbO or H 3bO 3-PbO mixes, be heated to temperature 650-900 DEG C with the temperature rise rate of temperature 1-30 DEG C/h, constant temperature 5-80 hour, obtains mixed molten liquid, be cooled to temperature 610-830 DEG C again, wherein the mol ratio of containing barium compound, barium fluoride and boric acid and fusing assistant is 2: 1: 6: 1-6;
B, prepare barium fluoborate 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 barium fluoborate 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, barium fluoborate non-linear optic crystal can be obtained.
3. method according to claim 2, is characterized in that fusing assistant NaF-H 3bO 3naF and H in system 3bO 3mol ratio be 1-5: 3-6; In LiF-PbO or NaF-PbO system, the mol ratio of fluorochemical and plumbous oxide is 1-5: 1-6; 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 2in O-PbO system, the mol ratio of sodium oxide and plumbous oxide is 1-5: 0.1-6.
4. the purposes of barium fluoborate non-linear optic crystal according to claim 1 in preparation times frequency generator, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
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