CN104651933A - Chlorine barium borate, chlorine barium borate nonlinear optical crystal, and preparation method and uses of chlorine barium borate nonlinear optical crystal - Google Patents

Chlorine barium borate, chlorine barium borate nonlinear optical crystal, and preparation method and uses of chlorine barium borate nonlinear optical crystal Download PDF

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CN104651933A
CN104651933A CN201310591017.4A CN201310591017A CN104651933A CN 104651933 A CN104651933 A CN 104651933A CN 201310591017 A CN201310591017 A CN 201310591017A CN 104651933 A CN104651933 A CN 104651933A
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CN104651933B (en
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潘世烈
李弘毅
鹿毅
俞洪伟
吴红萍
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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    • C30B29/10—Inorganic compounds or compositions
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
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    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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Abstract

The present invention relates to a compound chlorine barium borate, a chlorine barium borate nonlinear optical crystal, and a preparation method and uses of the chlorine barium borate nonlinear optical crystal. According to the present invention, the chemical formula of the compound is Ba7B3O11Cl, the molecular weight is 1205.26, and the compound is synthesized by adopting a solid phase reaction method; the chemical formula of the chlorine barium borate nonlinear optical crystal is Ba7B3O11Cl, the molecular weight is 1205.26, the crystal does not have the symmetry center and belongs to the hexagonal crystal system, the space group is P6[3]mc, and the cell parameters are as the follows: a is 11.2266 (17) angstrom, c is 7.214 (2) angstrom, Z is 2, and V is 787.4 (3) angstrom; the frequency doubling effect of the crystal powder achieves the 0.5 time of the KDP (KH2PO4); and the crystal has characteristics of large mechanical hardness, easy cutting, easy polish processing and easy preservation, and is widely applied in preparation of frequency doubling generators, frequency up-convertors, frequency down-convertors, or optical parameter oscillators and other nonlinear optical devices.

Description

Chloroboric acid barium and chloroboric acid barium non-linear optic crystal and preparation method and purposes
Technical field
The present invention relates to compound chloroboric acid barium Ba 7b 3o 11cl and chloroboric acid barium non-linear optic crystal and preparation method and the device for non-linear optical utilizing this crystal to make.
Background technology
Ultraviolet nonlinear optical material is the critical material that solid laser produces Ultraviolet Coherent Light, in order to obtain the nonlinear optical material with nonlinear optical property, method conventional in the world at present introduces the nonlinear optics functional motif easily making it produce distortion in the structure, and these primitives mainly contain containing d 0, d 10the transition-metal cation polyhedron of electronic structure or the metallic cation polyhedron containing lone electron pair.But these structural motifs usually make the ultraviolet cut-on limit red shift of material, make it to be used for ultraviolet region.And boratory feature be exactly be conducive to uv-radiation through, in borate oneself through having found many outstanding non-linear optic crystals, such as BBO(β-BBO), LBO(LiB 3o 5) crystal, CBO(CsB 3o 5) crystal, CLBO(CsLiB 6o 10) crystal and KBBCL(KBe 2bO 3cL 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, synthesize new non-linear optical crystal material and remain an extremely important and large order.
When Development of Novel ultraviolet non-linear optic crystal, people still select transparency range wide, the borate crystal that laser damage threshold is large, and in order to further widen transparency range, its ultraviolet cut-on limit is made to reach deep ultraviolet, positively charged ion uses the basic metal or alkaline-earth metal that do not have d-d transition of electron usually, and introduces halide-ions in borate skeleton.
Summary of the invention
The object of the invention is to provide a kind of compound chloroboric acid barium, and this compound chemistry formula is Ba 7b 3o 11cl, molecular weight 1205.26, adopts solid reaction process synthetic compound.
Another object of the present invention is to provide a kind of chloroboric acid barium non-linear optic crystal, and the chemical formula of this crystal is Ba 7b 3o 11cl, molecular weight 1205.26, does not have symmetry centre, belongs to hexagonal system, spacer P6 3mc, unit cell parameters is z=2,
Still a further object of the present invention is to provide the preparation method adopting solid reaction process synthetic compound and high temperature solution method growth chloroboric acid barium non-linear optic crystal.
Another object of the present invention is the purposes providing a kind of chloroboric acid barium 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 chloroboric acid barium of the present invention, the chemical formula of this compound is Ba 7b 3o 11cl, molecular weight 1205.26, adopts solid reaction process synthetic compound.
A kind of compound chloroboric acid barium non-linear optic crystal, the chemical formula of this crystal is Ba 7b 3o 11cl, molecular weight 1205.26, does not have symmetry centre, belongs to hexagonal system, spacer P6 3mc, unit cell parameters is z=2,
The preparation method of described compound chloroboric acid barium non-linear optic crystal, adopt solid reaction process synthetic compound and high temperature solution method growing crystal, concrete operations follow these steps to carry out:
A, by baric, chloride and boron-containing compound 9: 1: 3-6 takes and puts into mortar 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 650 DEG C, constant temperature 24 hours, be cooled to room temperature, take out and put into retort furnace after second time grinding, be warming up to 750 DEG C again, constant temperature 24 hours, be cooled to room temperature, take out and put into retort furnace after third time grinding, be warming up to 900 DEG C again, constant temperature 48 hours, take out and obtain chloroboric acid barium compound single-phase polycrystalline powder through grinding, again X-ray analysis is carried out to this product, gained X-ray spectrogram and chloroboric acid barium Ba 7b 3o 11the X-ray spectrogram that Cl single crystal structure obtains is consistent,
B, the single-phase polycrystalline powder obtained by step a mix with fusing assistant, temperature 650-1200 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 610-1000 DEG C again, wherein the mol ratio of chloroboric acid barium compound single-phase polycrystalline powder and fusing assistant is 1: 1-12;
Or directly baric, chloride and boron-containing compound are mixed with fusing assistant, temperature 650-1200 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 610-1000 DEG C again, wherein baric, chloride and boron-containing compound and fusing assistant mol ratio are 9: 1: 6: 1-12;
C, prepare chloroboric acid barium seed crystal: the mixed molten liquid obtained by step b is slowly down to room temperature with the speed of temperature 0.5-10 DEG C/h, spontaneous crystallization obtains chloroboric acid barium seed crystal;
D, the crucible filling the mixed molten liquid that step b obtains is inserted in crystal growing furnace, the seed crystal obtained by step c is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 5-60 minute, by seed crystal down to contacting mixed molten liquid liquid surface or carry out melt back in mixed molten liquid, constant temperature 5-60 minute, is down to temperature 750-945 DEG C with the speed of temperature 1-60 DEG C/h;
E, 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, chloroboric acid barium 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; Chlorine-containing compound is bariumchloride; Boron-containing compound is H 3bO 3or B 2o 3.
Fusing assistant described in step b is NaCL-H 3bO 3, H 3bO 3-Na 2o, Na 2o-PbO, LiCl-PbO, NaCl-PbO or H 3bO 3-PbO.
Step b fusing assistant NaCl-H 3bO 3naCl and H in system 3bO 3mol ratio be 1-5: 3-6; In LiCl-PbO or NaCl-PbO system, the mol ratio of muriate 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.
Described chloroboric acid barium non-linear optic crystal is in the purposes of preparation times frequency generator, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
Compound chloroboric acid barium of the present invention and chloroboric acid barium non-linear optic crystal and preparation method and purposes, wherein compound chloroboric acid barium Ba 7b 3o 11cl and the patent No. 201010553377.1 chemical formula Ba 2b 5o 9it is completely different that Cl compares its structure.Although Ba 2b 5o 9cl and Ba 7b 3o 11containing identical element in Cl structure, but two structures but have diverse crystalline structure, first, and Ba 2b 5o 9cl crystallization, in orthogonal PNN2 spacer, is biaxal crystal, and Ba 7b 3o 11cl then crystallization, in the P63MC spacer of six sides, is that single shaft is brilliant.Both structures also have many differences, as Ba 2b 5o 9in Cl, the content of B is higher, and B-O group has been interconnected to form three-dimensional network, and for Ba 7b 3o 11cl, B-O group is then isolated BO 3trilateral.In sum, although Ba 2b 5o 9cl and Ba 7b 3o 11containing identical element in Cl structure, but they are diverse crystalline structure.
Chloroboric acid barium compound of the present invention, its chemical formula is Ba 7b 3o 11cl; Solid reaction process is adopted to prepare chloroboric acid barium compound by following chemical equation:
(1)13BaCO 3+BaCl 2+6H 3BO 3→2Ba 7B 3O 11Cl+13CO 2↑+9H 2O↑
(2)13Ba(NO 3) 2+BaCl 2+6H 3BO 3→2Ba 7B 3O 11Cl+26NO 2↑+6.5O 2+9H 2O↑
(3)13BaO+BaCl 2+6H 3BO 3→2Ba 7B 3O 11Cl+9H 2O↑
(4)13Ba(OH) 2+BaCl 2+6H 3BO 3→2Ba 7B 3O 11Cl+22H 2O↑
(5)13Ba(HCO 3) 2+BaCl 2+6H 3BO 3→2Ba 7B 3O 11Cl+26CO 2↑+22H 2O↑
(6)13BaCO 3+BaCl 2+3B 2O 3→2Ba 7B 3O 11Cl+13CO 2↑
(7)13Ba(NO 3) 2+BaCl 2+3B 2O 3→2Ba 7B 3O 11Cl+26NO 2↑+6.5O 2↑
(8)13BaO+BaCl 2+3B 2O 3→2Ba 7B 3O 11Cl
(9)13Ba(OH) 2+BaCl 2+3B 2O 3→2Ba 7B 3O 11Cl+13H 2O↑
(10)13Ba(HCO 3) 2+BaCl 2+3B 2O 3→2Ba 7B 3O 11Cl+26CO 2↑+13H 2O↑
(11)13BaC 2O 4+BaCl 2+3B 2O 3→2Ba 7B 3O 11Cl+13CO 2↑+13CO↑。
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 chloroboric acid barium 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) 0.5 times.
Accompanying drawing explanation
Fig. 1 is Ba of the present invention 7b 3o 11the X-ray diffraction figure of Cl powder.
Fig. 2 is Ba of the present invention 7b 3o 11the fundamental diagram of the device for non-linear optical that Cl crystal makes, wherein 1 is laser apparatus, and 2 for sending light beam, and 3 is Ba 7b 3o 11cl crystal, 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: 13BaCO 3+ BaCl 2+ 6H 3bO 3→ 2Ba 7b 3o 11cl+13CO 2↑+9H 2o ↑ synthesis Ba 7b 3o 11cl compound:
By BaCO 3, BaCl 2, H 3bO 3take put into mortar at 9: 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 650 DEG C, constant temperature 24 hours, be cooled to room temperature, take out and put into retort furnace after second time grinding, be warming up to 750 DEG C again, constant temperature 24 hours, be cooled to room temperature, take out and put into retort furnace after third time grinding, be warming up to 900 DEG C again, constant temperature 48 hours, take out through grinding obtained chloroboric acid barium compound single-phase polycrystalline powder, X-ray analysis is carried out to this product, gained X-ray spectrogram and chloroboric acid barium Ba 7b 3o 11the X-ray spectrogram that Cl single crystal structure obtains is consistent,
By the chloroboric acid barium Ba obtained 7b 3o 11cl compound single-phase polycrystal powder and fusing assistant NaCl-H 3bO 3ba in molar ratio 7b 3o 11cl: NaCl-H 3bO 3=1: 3, wherein NaCl and H 3bO 3mol ratio be 3: 4, carry out mixture, load in the opening platinum crucible of Φ 80mm × 80mm, be heated to 900 DEG C with the temperature rise rate of temperature 30 DEG C/h, constant temperature 15 hours, obtains mixed molten liquid, then is cooled to 840 DEG C;
Prepare chloroboric acid barium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of temperature 0.5 DEG C/h to room temperature, spontaneous crystallization obtains chloroboric acid barium seed crystal;
Growing crystal in compound liquation: by the Ba obtained 7b 3o 11cl seed 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 850 DEG C;
Again with the cooling of the speed of temperature 2 DEG C of/day, with the rotating speed rotary seed crystal rod of 10rpm, after crystal growth terminates, make crystal depart from liquid level, be down to room temperature with the speed of temperature 10 DEG C/h, the Ba being of a size of 56mm × 40mm × 30mm can be obtained 7b 3o 11cl crystal.
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: 13Ba (NO 3) 2+ BaCl 2+ 6H 3bO 3→ 2Ba 7b 3o 11cl+26NO 2↑+6.5O 2+ 9H 2o ↑ synthesis Ba 7b 3o 11cl compound:
By Ba (NO 3) 2, BaCl 2, H 3bO 3directly take raw material at 9: 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 850 DEG C, constant temperature 60 hours, obtains mixed molten liquid, is cooling to temperature 815 DEG C;
Prepare chloroboric acid barium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of temperature 1.5 DEG C/h to room temperature, spontaneous crystallization obtains chloroboric acid barium seed crystal;
By the Ba obtained 7b 3o 11cl seed crystal is fixed on seed rod, seed crystal from crystal growing furnace top, 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 810 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 7b 3o 11cl crystal.
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: 13BaO+BaCl 2+ 6H 3bO 3→ 2Ba 7b 3o 11cl+9H 2o ↑ synthesis Ba 7b 3o 11cl compound:
By BaO, BaCl 2, H 3bO 3put into mortar at 9: 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 900 DEG C constant temperature 48 hours again in retort furnace, taken out, put into mortar and smash grinding to pieces and namely obtain Ba 7b 3o 11cl compound, carries out X-ray analysis to this product, gained X-ray spectrogram and chloroboric acid barium Ba 7b 3o 11the X-ray spectrogram that Cl single crystal structure obtains is consistent;
By the Ba of synthesis 7b 3o 11cl compound and fusing assistant LiCl-PbO are in molar ratio=1: 5, and wherein the mol ratio of LiCl and PbO is carry out mixture at 1: 1, load in the opening platinum crucible of Φ 80mm × 80mm, be warming up to temperature 920 DEG C, constant temperature 80 hours, obtains mixed molten liquid, then is down to temperature 860 DEG C;
Prepare chloroboric acid barium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of temperature 2.5 DEG C/h to room temperature, spontaneous crystallization obtains chloroboric acid barium seed crystal;
Be fixed on by the seed crystal of acquisition from seed crystal crystal growing furnace top on seed rod, first at mixed molten liquid preheating seed crystal 10 minutes on the surface, under part immersed in liquid level, make seed crystal carry out melt back in mixed molten liquid, constant temperature 20 minutes, fast cooling is to temperature 750 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 7b 3o 11cl crystal.
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: 13Ba (OH) 2+ BaCl 2+ 6H 3bO 3→ 2Ba 7b 3o 11cl+22H 2o ↑ synthesis Ba 7b 3o 11cl compound:
By Ba (OH) 2, BaCl 2and H 3bO 3directly take raw material at 9: 1: 6 in molar ratio, by the raw material that takes and fusing assistant NaCl-H 3bO 3carry out mixture at 1: 3 in molar ratio, wherein NaCl and H 3bO 3mol ratio be 1: 1, load in the opening platinum crucible of Φ 80mm × 80mm, be warming up to temperature 865 DEG C, constant temperature 10 hours, obtains mixed molten liquid, is cooling to temperature 815 DEG C;
Prepare chloroboric acid barium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of temperature 2.5 DEG C/h to room temperature, spontaneous crystallization obtains chloroboric acid barium seed crystal;
By the Ba obtained 7b 3o 11cl seed 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 800 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 7b 3o 11cl crystal.
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: 13Ba (HCO 3) 2+ BaCl 2+ 6H 3bO 3→ 2Ba 7b 3o 11cl+26CO 2↑+22H 2o ↑ synthesis Ba (HCO 3) 2compound:
By Ba (HCO 3) 2, BaCl 2, H 3bO 3directly take raw material at 9: 1: 6 in molar ratio, by the raw material that takes and fusing assistant NaCl-PbO in molar ratio 1: 6, carry out mixture, wherein NaCl and PbO mol ratio is 3: 1, load in the opening platinum crucible of Φ 80mm × 80mm, be warming up to temperature 880 DEG C, constant temperature 60 hours, obtain mixed molten liquid, then be down to temperature 820 DEG C;
Prepare chloroboric acid barium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of temperature 3.5 DEG C/h to room temperature, spontaneous crystallization obtains chloroboric acid barium seed crystal;
By the Ba obtained 7b 3o 11cl seed 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 815 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 7b 3o 11cl crystal.
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: 9BaCO 3+ BaCl 2+ 3B 2o 3→ 2Ba 7b 3o 11cl+9CO 2↑ synthesis Ba 7b 3o 11cl compound:
By BaCO 3, BaCl 2, B 2o 3directly take raw material at 9: 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 850 DEG C, constant temperature 80 hours, obtains mixed molten liquid, then is down to temperature 815 DEG C;
Prepare chloroboric acid barium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of temperature 5 DEG C/h to room temperature, spontaneous crystallization obtains chloroboric acid barium seed crystal;
By the Ba obtained 7b 3o 11cl seed crystal is fixed on from seed crystal crystal growing furnace top on seed rod, and first preheating seed crystal 20 minutes, carries out melt back by seed crystal on the surface down to mixed molten liquid, constant temperature 5 minutes, and fast cooling is to temperature 810 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 7b 3o 11cl crystal.
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: 13Ba (NO 3) 2+ BaCl 2+ 3B 2o 3→ 2Ba 7b 3o 11cl+26NO 2↑+6.5O 2↑ synthesis Ba 7b 3o 11cl compound;
By Ba (NO 3) 2, BaCl 2, B 2o 3directly take raw material at 9: 1: 3 in molar ratio, the raw material taken and fusing assistant NaCl-PbO are carried out mixture in molar ratio at 1: 2, wherein NaCl and PbO mol ratio is in the opening platinum crucible of 3: 2 loading Φ 80mm × 80mm, be warming up to temperature 960 DEG C, constant temperature 80 hours, obtain mixed molten liquid, then be down to temperature 910 DEG C;
Prepare chloroboric acid barium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of temperature 10 DEG C/h to room temperature, spontaneous crystallization obtains chloroboric acid barium seed crystal;
Be fixed on by the seed crystal of acquisition from seed crystal crystal growing furnace top on seed rod, first preheating seed crystal 25 minutes, make seed crystal carry out melt back down to mixed molten liquid surface, constant temperature 25 minutes, fast cooling is to temperature 900 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 7b 3o 11cl crystal.
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: 13BaO+BaCl 2+ 3B 2o 3→ 2Ba 7b 3o 11cl compound;
By BaO, BaCl 2, B 2o 3put into mortar at 9: 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 750 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 980 DEG C constant temperature 48 hours again in retort furnace, taken out, put into mortar and smash grinding to pieces and namely obtain Ba 7b 3o 11cl compound, carries out X-ray analysis to this product, gained X-ray spectrogram and chloroboric acid barium Ba 7b 3o 11the X-ray spectrogram that Cl single crystal structure obtains is consistent;
Then by the Ba of synthesis 7b 3o 11cl compound 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 970 DEG C, constant temperature 70 hours, obtains mixed molten liquid, then is down to temperature 925 DEG C;
Prepare chloroboric acid barium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of temperature 4.0 DEG C/h to room temperature, spontaneous crystallization obtains chloroboric acid barium seed crystal;
By the Ba obtained 7b 3o 11cl seed crystal is fixed on from seed crystal crystal growing furnace top on seed rod, and first preheating seed crystal 8 minutes makes seed crystal carry out melt back down to mixed molten liquid surface, constant temperature 8 minutes, and fast cooling is to temperature 920 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 7b 3o 11cl crystal.
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: 13Ba (OH) 2+ BaCl 2+ 3B 2o 3→ 2Ba 7b 3o 11cl+13H 2o ↑ synthesis Ba 7b 3o 11cl compound:
By Ba (OH) 2, BaCl 2, B 2o 3put into mortar at 9: 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 750 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 980 DEG C constant temperature 48 hours again in retort furnace, taken out, put into mortar and smash grinding to pieces and namely obtain Ba 7b 3o 11cl compound, carries out X-ray analysis to this product, gained X-ray spectrogram and chloroboric acid barium Ba 7b 3o 11the X-ray spectrogram that Cl single crystal structure obtains is consistent;
Then by the Ba of synthesis 7b 3o 11cl compound 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 830 DEG C, constant temperature 45 hours, obtains mixed molten liquid, then is down to temperature 820 DEG C;
Prepare chloroboric acid barium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of temperature 6.5 DEG C/h to room temperature, spontaneous crystallization obtains chloroboric acid barium seed crystal;
By the Ba obtained 7b 3o 11cl seed crystal is fixed on from seed crystal crystal growing furnace top on seed rod, and first preheating seed crystal 15 minutes makes seed crystal carry out melt back down to mixed molten liquid surface, constant temperature 15 minutes, and fast cooling is to temperature of saturation 815 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 7b 3o 11cl crystal.
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: 13Ba (HCO 3) 2+ BaCl 2+ 3B 2o 3→ 2Ba 7b 3o 11cl+26CO 2↑+13H 2o ↑ synthesis Ba 7b 3o 11cl compound:
By Ba(HCO 3) 2, BaCl 2, B 2o 3put into mortar at 9: 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 750 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 980 DEG C constant temperature 48 hours again in retort furnace, taken out, put into mortar and smash grinding to pieces and namely obtain Ba 7b 3o 11cl compound, carries out X-ray analysis to this product, gained X-ray spectrogram and chloroboric acid barium Ba 7b 3o 11the X-ray spectrogram that Cl single crystal structure obtains is consistent; ,
By the Ba of synthesis 7b 3o 11cl compound and fusing assistant NaCl-PbO carry out mixture in molar ratio at 3: 2, and wherein NaCl and PbO mol ratio is 2: 1, and load in the opening platinum crucible of Φ 80mm × 80mm, be warming up to temperature 1100 DEG C, constant temperature obtains mixed molten liquid in 5 hours, then is down to temperature 950 DEG C;
Prepare chloroboric acid barium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of temperature 4.0 DEG C/h to room temperature, spontaneous crystallization obtains chloroboric acid barium seed crystal;
By the Ba obtained 7b 3o 11cl seed crystal is fixed on from seed crystal crystal growing furnace top on seed rod, and first preheating seed crystal 20 minutes makes seed crystal carry out melt back down to mixed molten liquid surface, constant temperature 25 minutes, and fast cooling is to temperature 945 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 7b 3o 11cl crystal.
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: 13BaC 2o 4+ BaCl 2+ 3B 2o 3→ 2Ba 7b 3o 11cl+13CO 2↑+13CO ↑ synthesis Ba 7b 3o 11cl compound:
By BaC 2o 4, BaCl 2, B 2o 39:1:3 puts into mortar in molar ratio, and 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 750 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 980 DEG C constant temperature 48 hours again in retort furnace, taken out, put into mortar and smash grinding to pieces and namely obtain Ba 7b 3o 11cl compound, carries out X-ray analysis to this product, gained X-ray spectrogram and chloroboric acid barium Ba 7b 3o 11the X-ray spectrogram that Cl single crystal structure obtains is consistent; ,
By the Ba of synthesis 7b 3o 11cl compound and fusing assistant H 3bO 3-PbO in molar ratio 1:3 carries out mixture, wherein H 3bO 3be 5:1 with PbO mol ratio, load in the opening platinum crucible of Φ 80mm × 80mm, be warming up to temperature 1000 DEG C, constant temperature obtains mixed molten liquid in 50 hours, then is down to temperature 920 DEG C;
Prepare chloroboric acid barium seed crystal: by the mixed molten liquid that obtains with the speed slow cooling of temperature 10 DEG C/h to room temperature, spontaneous crystallization obtains chloroboric acid barium seed crystal;
By the Ba obtained 7b 3o 11cl seed crystal is fixed on from seed crystal crystal growing furnace top on seed rod, and first preheating seed crystal 20 minutes makes seed crystal carry out melt back down to mixed molten liquid surface, constant temperature 25 minutes, is cooled to temperature of saturation 915 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 7b 3o 11cl crystal.
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 7b 3o 11cl crystal 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 Q Nd:YAG laser apparatus 1 is that Ba injected by the infrared beam 2 of 1064nm 7b 3o 11cl monocrystalline 3, produce the green frequency doubled light that wavelength is 532nm, output intensity is 0.5 times of equal conditions KDP, and outgoing beam 4 is the infrared light of 1064nm and the green glow of 532nm containing wavelength, after filter plate 5 elimination, obtain the green laser that wavelength is 532nm.

Claims (7)

1. a compound chloroboric acid barium, is characterized in that the chemical formula of this compound is Ba 7b 3o 11cl, molecular weight 1205.26, adopts solid reaction process synthetic compound.
2. a compound chloroboric acid barium non-linear optic crystal, is characterized in that the chemical formula of this crystal is Ba 7b 3o 11cl, molecular weight 1205.26, does not have symmetry centre, belongs to hexagonal system, spacer p6 3 mc, unit cell parameters is a=11.2266 (17), c=7.214 (2). and Z=2, V=787.4 (3) 3.
3. the preparation method of compound chloroboric acid barium non-linear optic crystal according to claim 2, it is characterized in that adopting solid reaction process synthetic compound and high temperature solution method growing crystal, concrete operations follow these steps to carry out:
A, by baric, chloride and boron-containing compound in molar ratio 9:1:3-6 takes and puts into mortar, 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 650 DEG C, constant temperature 24 hours, be cooled to room temperature, take out and put into retort furnace after second time grinding, be warming up to 750 DEG C again, constant temperature 24 hours, be cooled to room temperature, take out and put into retort furnace after third time grinding, be warming up to 900 DEG C again, constant temperature 48 hours, take out and obtain chloroboric acid barium compound single-phase polycrystalline powder through grinding, again X-ray analysis is carried out to this product, gained X-ray spectrogram and chloroboric acid barium Ba 7b 3o 11the X-ray spectrogram that Cl single crystal structure obtains is consistent,
B, the single-phase polycrystalline powder obtained by step a mix with fusing assistant, temperature 650-1200 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 610-1000 DEG C again, wherein the mol ratio of chloroboric acid barium compound single-phase polycrystalline powder and fusing assistant is 1:1-12;
Or directly baric, chloride and boron-containing compound are mixed with fusing assistant, temperature 650-1200 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 610-1000 DEG C again, wherein baric, chloride and boron-containing compound and fusing assistant mol ratio are 9:1:6:1-12;
C, prepare chloroboric acid barium seed crystal: the mixed molten liquid obtained by step b is slowly down to room temperature with the speed of temperature 0.5-10 DEG C/h, spontaneous crystallization obtains chloroboric acid barium seed crystal;
D, the crucible filling the mixed molten liquid that step b obtains is inserted in crystal growing furnace, the seed crystal obtained by step c is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 5-60 minute, by seed crystal down to contacting mixed molten liquid liquid surface or carry out melt back in mixed molten liquid, constant temperature 5-60 minute, is down to temperature 750-945 DEG C with the speed of temperature 1-60 DEG C/h;
E, 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, chloroboric acid barium non-linear optic crystal can be obtained.
4. method according to claim 3, is characterized in that containing barium compound described in step a is barium carbonate, nitrate of baryta, barium oxide, hydrated barta, barium bicarbonate or barium oxalate; Chlorine-containing compound is bariumchloride; Boron-containing compound is H 3bO 3or B 2o 3.
5. method according to claim 3, is characterized in that fusing assistant described in step b is NaCL-H 3bO 3, H 3bO 3-Na 2o, Na 2o-PbO, LiCl-PbO, NaCl-PbO or H 3bO 3-PbO.
6. method according to claim 5, is characterized in that step b fusing assistant NaCl-H 3bO 3naCl and H in system 3bO 3mol ratio be 1-5:3-6; In LiCl-PbO or NaCl-PbO system, the mol ratio of muriate 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.
7. chloroboric acid barium non-linear optic crystal according to claim 2 is in the purposes of preparation times frequency generator, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
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