CN104651933B - 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 PDFInfo
- Publication number
- CN104651933B CN104651933B CN201310591017.4A CN201310591017A CN104651933B CN 104651933 B CN104651933 B CN 104651933B CN 201310591017 A CN201310591017 A CN 201310591017A CN 104651933 B CN104651933 B CN 104651933B
- Authority
- CN
- China
- Prior art keywords
- crystal
- barium
- temperature
- compound
- pbo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- 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
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
- C30B9/12—Salt solvents, e.g. flux growth
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- 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
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/3551—Crystals
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
Technical field
The present invention relates to compound chloroboric acid barium Ba7B3O11Cl and chloroboric acid barium nonlinear optical crystal and preparation method and
The device for non-linear optical made using the crystal.
Background technology
Ultraviolet nonlinear optical material is the critical material that solid-state laser produces Ultraviolet Coherent Light, in order to obtain with non-
The nonlinear optical material of linear optics property, at present method conventional in the world is to introduce easily make its generation distortion in the structure
Nonlinear optics functional motif, these primitives mainly have containing d0, d10The transition-metal cation polyhedron of electronic structure or
Metal cation polyhedron containing lone electron pair.However, these structural motifs usually make the ultraviolet cut-on side red shift of material, it is allowed to
Cannot be used for ultra-violet (UV) band.And boratory feature is just advantageous for the transmission of ultraviolet radioactive, oneself is it is found that permitted in the borate
More outstanding nonlinear optical crystal, such as BBO (β-BBO), LBO (LiB3O5) crystal, CBO (CsB3O5) crystal, CLBO
(CsLiB6O10) crystal and KBBCL (KBe2BO3CL2) crystal.Although the crystal technique of these materials reaches its maturity,
There are still clearly disadvantageous part:Such as the easy deliquescence of crystal, growth cycle length, layer growth habit are serious and expensive.
Therefore, synthesize new non-linear optical crystal material and remain that one extremely important and large order.
In the ultraviolet nonlinear optical crystal of Development of Novel, people still select transparency range width, and laser damage threshold is big
Borate crystal, and in order to further widen transparency range so as to which ultraviolet cut-on side can reach deep ultraviolet, cation is led to
Often using the alkali metal without d-d electron transitions or alkaline-earth metal, and halide ion is introduced in borate skeleton.
The content of the invention
Present invention aim at providing a kind of compound chloroboric acid barium, the compound chemical formula is Ba7B3O11Cl, molecular weight
1205.26, compound is synthesized using solid reaction process.
Another object of the present invention is to provide a kind of chloroboric acid barium nonlinear optical crystal, and the chemical formula of the crystal is
Ba7B3O11Cl, molecular weight 1205.26, not with symmetrical centre, belongs to hexagonal crystal system, space group P63Mc, cell parameter is
Still a further object of the present invention is to provide to synthesize compound and high temperature solution method growth chloroboric acid using solid reaction process
The preparation method of barium nonlinear optical crystal.
Another object of the present invention is to provide a kind of purposes of chloroboric acid barium device for non-linear optical, for preparing frequency multiplication
Generator, up or down frequency converter or optical parametric oscillator.
A kind of compound chloroboric acid barium of the present invention, the chemical formula of the compound is Ba7B3O11Cl, molecular weight
1205.26, compound is synthesized using solid reaction process.
A kind of compound chloroboric acid barium nonlinear optical crystal, the chemical formula of the crystal is Ba7B3O11Cl, molecular weight
1205.26, not with symmetrical centre, belong to hexagonal crystal system, space group P63Mc, cell parameter is
The preparation method of the compound chloroboric acid barium nonlinear optical crystal, using solid reaction process synthesize compound and
High temperature solution method grows crystal, and concrete operations follow these steps to carry out:
A, by baric, chloride and boron-containing compound in molar ratio 9:1:3-6 is weighed and is put in mortar, and mixing is simultaneously carefully ground
Mill, in being then charged into the opening corundum crucible of Φ 100mm × 100mm, in being put into Muffle furnace, is to slowly warm up to 650 DEG C, constant temperature 24
Hour, it is cooled to room temperature, take out after Jing grinds for second and be put in Muffle furnace, then it is warming up to 750 DEG C, constant temperature 24 hours is cold
But to room temperature, take out Jing after third time is ground and be put in Muffle furnace, then be warming up to 900 DEG C, constant temperature 48 hours takes out ground
To chloroboric acid barium compound single-phase polycrystalline powder, then X-ray analyses are carried out to the product, gained X-ray spectrogram and chloroboric acid barium
Ba7B3O11The X-ray spectrogram that Cl mono-crystalline structures are obtained is consistent;
B, the single-phase polycrystalline powder that step a is obtained is mixed homogeneously with flux, with the heating rate of temperature 1-30 DEG C/h
Temperature 650-1200 DEG C is heated to, constant temperature 5-80 hours obtain mixed molten liquid, then are cooled to temperature 610-1000 DEG C, wherein chlorine
Barium borate compound single-phase polycrystal powder is 1 with the mol ratio of flux:1-12;
Or directly baric, chloride and boron-containing compound are mixed homogeneously with flux, with the intensification speed of temperature 1-30 DEG C/h
Rate is heated to temperature 650-1200 DEG C, and constant temperature 5-80 hours obtain mixed molten liquid, then are cooled to temperature 610-1000 DEG C, wherein
The mol ratio of baric, chloride and boron-containing compound and flux is 9:1:6:1-12;
C, prepare chloroboric acid barium seed crystal:The mixed molten liquid that step b is obtained slowly is dropped with the speed of temperature 0.5-10 DEG C/h
To room temperature, spontaneous crystallization obtains chloroboric acid barium seed crystal;
D, the crucible for filling mixed molten liquid obtained in step b is inserted in crystal growing furnace, the seed crystal that step c is obtained is consolidated
On seed rod, from the lower seed crystal in crystal growing furnace top, seed crystal 5-60 minutes are first preheated, by seed crystal down to contact mixed molten liquid
Liquid surface carries out melt back down in mixed molten liquid, constant temperature 5-60 minutes, with the speed of temperature 1-60 DEG C/h temperature 750- is down to
945℃;
E, again with temperature 0.1-5 DEG C/day speed slow cooling, crystal is carried out with 0-60rpm rotating speeds rotary seed crystal rod
Growth, after crystal growth to required yardstick, by crystal lift-off mixed molten liquid surface, and is down to room with temperature 1-80 DEG C/h speed
Temperature, then takes out crystal from burner hearth, you can obtain chloroboric acid barium nonlinear optical crystal.
Containing barium compound described in step a is brium carbonate, barium nitrate, Barium monoxide, barium hydroxide, barium bicarbonate or barium oxalate;
Chlorine-containing compound is barium chloride;Boron-containing compound is H3BO3Or B2O3。
Flux described in step b is NaCl-H3BO3、H3BO3-Na2O、Na2O-PbO, LiCl-PbO, NaCl-PbO or
H3BO3-PbO。
Step b flux NaCl-H3BO3NaCl and H in system3BO3Mol ratio be 1-5:3-6;LiCl-PbO or
Chloride and the mol ratio of lead oxide are 1-5 in NaCl-PbO systems:1-6;H3BO3- PbO or H3BO3-Na2O system mesoboric acids
It is 2-5 with the mol ratio of oxide:1-5;Na2Sodium oxide and the mol ratio of lead oxide are 1-5 in O-PbO systems:0.1-6.
The chloroboric acid barium nonlinear optical crystal is preparing times frequency generator, upper frequency transducer, lower frequency transducer
Or the purposes of optical parametric oscillator.
Compound chloroboric acid barium of the present invention and chloroboric acid barium nonlinear optical crystal and preparation method and purposes, its
Middle compound chloroboric acid barium Ba7B3O11The Cl and chemical formula Ba of the patent No. 201010553377.12B5O9Cl compares its structure completely not
Together.Although Ba2B5O9Cl and Ba7B3O11Contain identical element in Cl structures, but two structures but have diverse crystal to tie
Structure, first, Ba2B5O9Cl is crystallized in orthogonal PNN2 space groups, is biaxal crystal, and Ba7B3O11Cl is then crystallized in six sides'
P63MC space groups, are that single shaft is brilliant.Both structures also have many differences, such as Ba2B5O9In Cl, the content of B is higher, B-O groups
Three-dimensional network has been interconnected to form, and for Ba7B3O11Cl, B-O group is then isolated BO3Triangle.In sum, to the greatest extent
Pipe Ba2B5O9Cl and Ba7B3O11Contain identical element in Cl structures, but they are diverse crystal structures.
Chloroboric acid barium compound of the present invention, its chemical formula is Ba7B3O11Cl;Followingization is pressed using solid reaction process
Learn reaction equation and prepare chloroboric acid barium compound:
(1)13BaCO3+BaCl2+6H3BO3→2Ba7B3O11Cl+13CO2↑+9H2O↑
(2)13Ba(NO3)2+BaCl2+6H3BO3→2Ba7B3O11Cl+26NO2↑+6.5O2+9H2O↑
(3)13BaO+BaCl2+6H3BO3→2Ba7B3O11Cl+9H2O↑
(4)13Ba(OH)2+BaCl2+6H3BO3→2Ba7B3O11Cl+22H2O↑
(5)13Ba(HCO3)2+BaCl2+6H3BO3→2Ba7B3O11Cl+26CO2↑+22H2O↑
(6)13BaCO3+BaCl2+3B2O3→2Ba7B3O11Cl+13CO2↑
(7)13Ba(NO3)2+BaCl2+3B2O3→2Ba7B3O11Cl+26NO2↑+6.5O2↑
(8)13BaO+BaCl2+3B2O3→2Ba7B3O11Cl
(9)13Ba(OH)2+BaCl2+3B2O3→2Ba7B3O11Cl+13H2O↑
(10)13Ba(HCO3)2+BaCl2+3B2O3→2Ba7B3O11Cl+26CO2↑+13H2O↑
(11)13BaC2O4+BaCl2+3B2O3→2Ba7B3O11Cl+13CO2↑+13CO↑。
Obtained crystal has wider transmission region, hardness is bigger, good mechanical property, not easily broken and deliquescence, it is easy to plus
The advantages of work and preservation.Using non-thread made by the compound chloroboric acid barium nonlinear optical crystal that the method for the invention is obtained
Property optics, at room temperature, uses Nd:YAG Q-switched lasers make light source, incident wavelength for 1064nm infrared light, output wavelength
For the green laser of 532nm, laser intensity is equivalent to KDP (KH2PO4) 0.5 times.
Description of the drawings
Fig. 1 is Ba of the present invention7B3O11The X-ray diffraction figure of Cl powder.
Fig. 2 is Ba of the present invention7B3O11The fundamental diagram of the device for non-linear optical that Cl crystal makes, wherein 1 is laser
Device, 2 to send light beam, and 3 is Ba7B3O11Cl crystal, 4 is outgoing beam, and 5 is filter plate.
Specific embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail:
Embodiment 1:
By reaction equation:13BaCO3+BaCl2+6H3BO3→2Ba7B3O11Cl+13CO2↑+9H2O ↑ synthesis Ba7B3O11Cl chemical combination
Thing:
By BaCO3、BaCl2、H3BO3In molar ratio 9:1:6 weigh and are put in mortar, and mixing is simultaneously carefully ground, and is then charged into
In the opening corundum crucible of Φ 100mm × 100mm, in being put into Muffle furnace, 650 DEG C are to slowly warm up to, constant temperature 24 hours is cooled to
Room temperature, takes out after Jing second grinds and is put in Muffle furnace, then is warming up to 750 DEG C, and constant temperature 24 hours is cooled to room temperature, takes
Go out Jing after third time is ground and be put in Muffle furnace, then be warming up to 900 DEG C, constant temperature 48 hours takes out ground prepared chloroboric acid barium
Compound single-phase polycrystal powder, X-ray analyses, gained X-ray spectrogram and chloroboric acid barium Ba are carried out to the product7B3O11Cl monocrystalline
The X-ray spectrogram that structure is obtained is consistent;
By the chloroboric acid barium Ba for obtaining7B3O11Cl compound single-phases polycrystal powder and flux NaCl-H3BO3In molar ratio
Ba7B3O11Cl:NaCl-H3BO3=1:3, wherein NaCl and H3BO3Mol ratio be 3:4, carry out mixture, load Φ 80mm ×
In the opening platinum crucible of 80mm, 900 DEG C are heated to the heating rate of 30 DEG C/h of temperature, constant temperature 15 hours is mixed
Liquation is closed, then is cooled to 840 DEG C;
Prepare chloroboric acid barium seed crystal:By the mixed molten liquid for obtaining with the speed slow cooling of 0.5 DEG C/h of temperature to room temperature, from
Send out crystallization and obtain chloroboric acid barium seed crystal;
Crystal is grown in compound liquation:The Ba that will be obtained7B3O11Cl seed crystals are fixed on seed rod from crystal growth
Furnace roof subordinate's seed crystal, first preheats seed crystal 10 minutes on mixed molten liquid surface, in immersed in liquid level, seed crystal is entered in mixed molten liquid
Row melt back, constant temperature 30 minutes, fast cooling to 850 DEG C of temperature;
Lowered the temperature with the speed of DEG C/day of temperature 2 again, with the rotating speed rotary seed crystal rod of 10rpm, after crystal growth terminates, made
Crystal departs from liquid level, and with 10 DEG C/h of speed of temperature room temperature is down to, you can acquisition size is 56mm × 40mm × 30mm's
Ba7B3O11Cl crystal.
Oxide spinel barium in reaction equation can be with Barium monoxide or barium nitrate or barium oxalate or barium hydroxide or barium bicarbonate
Replace, boric acid can be replaced by boron oxide.
Embodiment 2:
By reaction equation:13Ba(NO3)2+BaCl2+6H3BO3→2Ba7B3O11Cl+26NO2↑+6.5O2+9H2O ↑ synthesis
Ba7B3O11Cl compounds:
By Ba (NO3)2、BaCl2、H3BO3In molar ratio 9:1:6 directly weigh raw material, by the raw material for weighing and flux
Na2O-H3BO3In molar ratio 1:4 carry out mixture, wherein Na2O and H3BO3Mol ratio be 2:5, load opening for Φ 80mm × 80mm
In mouthful platinum crucible, 850 DEG C of temperature is warming up to, constant temperature 60 hours obtains mixed molten liquid, is being cooled to 815 DEG C of temperature;
Prepare chloroboric acid barium seed crystal:By the mixed molten liquid for obtaining with the speed slow cooling of 1.5 DEG C/h of temperature to room temperature, from
Send out crystallization and obtain chloroboric acid barium seed crystal;
The Ba that will be obtained7B3O11Cl seed crystals are fixed on seed rod, first molten in mixing from the lower seed crystal in crystal growing furnace top
Seed crystal 10 minutes is preheated on liquid surface, under immersed in liquid level, makes seed crystal carry out melt back in mixed molten liquid, constant temperature 30 minutes, quickly
It is cooled to 810 DEG C of temperature;
Again with the speed slow cooling of DEG C/day of temperature 1, not rotary seed crystal rod, after crystal growth to required yardstick, by crystalline substance
Body lift-off molten surface, with temperature 20 DEG C/h speed room temperature is down to, and then takes out crystal from burner hearth, you can obtaining size is
The Ba of 36mm × 22mm × 15mm7B3O11Cl crystal.
Raw material barium nitrate in reaction equation can be with brium carbonate or Barium monoxide or barium oxalate or barium hydroxide or barium bicarbonate
Replace, boric acid can be replaced by boron oxide.
Embodiment 3:
By reaction equation:13BaO+BaCl2+6H3BO3→2Ba7B3O11Cl+9H2O ↑ synthesis Ba7B3O11Cl compounds:
By BaO, BaCl2、H3BO3In molar ratio 9:1:6 are put in mortar, and mixing is simultaneously carefully ground, and is then charged into Φ
In the opening corundum crucible of 100mm × 100mm, compressed, in being put into Muffle furnace, be to slowly warm up to 550 DEG C, constant temperature 24 is little
When, crucible is taken out after cooling, now sample is more loose, then takes out sample and re-grinds uniformly, then is placed in crucible, in horse
Not it is drawn off in 900 DEG C of temperature constant temperature 48 hours again in stove, is put in mortar and smashs grinding to pieces and obtain final product Ba7B3O11Cl compounds,
X-ray analyses, gained X-ray spectrogram and chloroboric acid barium Ba are carried out to the product7B3O11The X-ray spectrogram that Cl mono-crystalline structures are obtained
It is consistent;
By the Ba of synthesis7B3O11Cl compounds are with flux LiCl-PbO in molar ratio=1:5, wherein LiCl are with PbO's
Mol ratio is 1:1 carries out mixture, in being fitted into the opening platinum crucible of Φ 80mm × 80mm, is warming up to 920 DEG C of temperature, and constant temperature 80 is little
When, mixed molten liquid is obtained, then it is down to 860 DEG C of temperature;
Prepare chloroboric acid barium seed crystal:By the mixed molten liquid for obtaining with the speed slow cooling of 2.5 DEG C/h of temperature to room temperature, from
Send out crystallization and obtain chloroboric acid barium seed crystal;
The seed crystal of acquisition is fixed on on seed rod seed crystal lower from crystal growing furnace top, it is first pre- on mixed molten liquid surface
Hot seed crystal 10 minutes, under being partly submerged in liquid level, makes seed crystal carry out melt back in mixed molten liquid, constant temperature 20 minutes, and fast cooling is extremely
750 DEG C of temperature;
Again with the speed slow cooling of DEG C/day of temperature 2, with the rotating speed rotary seed crystal rod of 30rpm, treat crystal growth to required
After yardstick, by crystal lift-off molten surface, room temperature is down to temperature 30 DEG C/h speed, is then taken out crystal from burner hearth, i.e.,
The Ba that size is 33mm × 30mm × 20mm can be obtained7B3O11Cl crystal.
Raw material Barium monoxide in reaction equation can be with brium carbonate or barium nitrate or barium oxalate or barium hydroxide or barium bicarbonate
Replace, boric acid can be replaced by boron oxide.
Embodiment 4:
By reaction equation:13Ba(OH)2+BaCl2+6H3BO3→2Ba7B3O11Cl+22H2O ↑ synthesis Ba7B3O11Cl compounds:
By Ba (OH)2、BaCl2And H3BO3In molar ratio 9:1:6 directly weigh raw material, by the raw material for weighing and flux
NaCl-H3BO3In molar ratio 1:3 carry out mixture, wherein NaCl and H3BO3Mol ratio be 1:1, load Φ 80mm × 80mm's
In opening platinum crucible, 865 DEG C of temperature is warming up to, constant temperature 10 hours obtains mixed molten liquid, is being cooled to 815 DEG C of temperature;
Prepare chloroboric acid barium seed crystal:By the mixed molten liquid for obtaining with the speed slow cooling of 2.5 DEG C/h of temperature to room temperature, from
Send out crystallization and obtain chloroboric acid barium seed crystal;
The Ba that will be obtained7B3O11Cl seed crystals are fixed on seed rod seed crystal lower from crystal growing furnace top, first molten in mixing
Seed crystal is preheated on liquid surface 5 minutes, under immersed in liquid level, make seed crystal that melt back, constant temperature 5 minutes, fast prompt drop are carried out in mixed molten liquid
Temperature is to 800 DEG C of temperature;
Then with the speed slow cooling of DEG C/day of temperature 2, with the rotating speed rotary seed crystal rod of 50rpm, treat crystal growth to institute
After needing yardstick, by crystal lift-off molten surface, room temperature is down to temperature 60 C/h speed, then takes out crystal from burner hearth,
Ba of the size for 30mm × 28mm × 15mm can be obtained7B3O11Cl crystal.
Raw material barium hydroxide in reaction equation can be with brium carbonate or barium nitrate or barium oxalate or Barium monoxide or barium bicarbonate
Replace, boric acid can be replaced by boron oxide.
Embodiment 5:
By reaction equation:13Ba(HCO3)2+BaCl2+6H3BO3→2Ba7B3O11Cl+26CO2↑+22H2O ↑ synthesis Ba (HCO3)2
Compound:
By Ba (HCO3)2、BaCl2、H3BO3In molar ratio 9:1:6 directly weigh raw material, by the raw material for weighing and flux
NaCl-PbO in molar ratio 1:6, mixture is carried out, wherein NaCl is 3 with PbO mol ratios:1, load the opening of Φ 80mm × 80mm
In platinum crucible, 880 DEG C of temperature is warming up to, constant temperature 60 hours obtains mixed molten liquid, then is down to 820 DEG C of temperature;
Prepare chloroboric acid barium seed crystal:By the mixed molten liquid for obtaining with the speed slow cooling of 3.5 DEG C/h of temperature to room temperature, from
Send out crystallization and obtain chloroboric acid barium seed crystal;
The Ba that will be obtained7B3O11Cl seed crystals are fixed on seed rod seed crystal lower from crystal growing furnace top, first molten in mixing
Seed crystal 15 minutes is preheated on liquid surface, under immersed in liquid level, makes seed crystal carry out melt back in mixed molten liquid, constant temperature 30 minutes, quickly
It is cooled to 815 DEG C of saturation temperature;
Again with the speed slow cooling of DEG C/day of temperature 3, seed crystal crucible is rotated with the rotating speed of 5rpm, treat crystal growth to institute
After needing yardstick, by crystal lift-off molten surface, room temperature is down to temperature 1 DEG C/h speed, is then taken out crystal from burner hearth, i.e.,
The Ba that size is 25mm × 24mm × 10mm can be obtained7B3O11Cl crystal.
Oxide spinel hydrogen barium in reaction equation can be with brium carbonate or barium nitrate or barium oxalate or barium hydroxide or Barium monoxide
Replace, boric acid can be replaced by boron oxide.
Embodiment 6:
By reaction equation:9BaCO3+BaCl2+3B2O3→2Ba7B3O11Cl+9CO2↑ synthesis Ba7B3O11Cl compounds:
By BaCO3、BaCl2、B2O3In molar ratio 9:1:3 directly weigh raw material, by the raw material for weighing and flux H3BO3-
PbO in molar ratio 1:6 carry out mixture, wherein H3BO3It is 3 with PbO mol ratios:1, load the opening platinum crucible of Φ 80mm × 80mm
In, 850 DEG C of temperature is warming up to, constant temperature 80 hours obtains mixed molten liquid, then is down to 815 DEG C of temperature;
Prepare chloroboric acid barium seed crystal:It is spontaneous by the mixed molten liquid for obtaining with the speed slow cooling of 5 DEG C/h of temperature to room temperature
Crystallization obtains chloroboric acid barium seed crystal;
The Ba that will be obtained7B3O11Cl seed crystals are fixed on seed rod seed crystal lower from crystal growing furnace top, first preheat seed crystal
20 minutes, seed crystal is carried out into melt back down on mixed molten liquid surface, constant temperature 5 minutes, fast cooling to 810 DEG C of temperature;
Then with the speed slow cooling of DEG C/day of temperature 3, with the rotating speed rotary seed crystal rod of 15rpm, treat crystal growth to institute
After needing yardstick, by crystals from molten surface, room temperature is down to temperature 15 DEG C/h speed, then takes out crystal from burner hearth,
Ba of the size for 35mm × 25mm × 20mm can be obtained7B3O11Cl crystal.
Raw material Barium monoxide in reaction equation can be with brium carbonate or barium nitrate or barium oxalate or barium hydroxide or barium bicarbonate
Replace, boron oxide can be replaced by boric acid.
Embodiment 7
By reaction equation:13Ba(NO3)2+BaCl2+3B2O3→2Ba7B3O11Cl+26NO2↑+6.5O2↑ synthesis Ba7B3O11Clization
Compound;
By Ba (NO3)2、BaCl2、B2O3In molar ratio 9:1:3 directly weigh raw material, by the raw material for weighing and flux
NaCl-PbO in molar ratio 1:2 carry out mixture, and wherein NaCl is 3 with PbO mol ratios:The 2 opening platinum for loading Φ 80mm × 80mm
In crucible, 960 DEG C of temperature is warming up to, constant temperature 80 hours obtains mixed molten liquid, then is down to 910 DEG C of temperature;
Prepare chloroboric acid barium seed crystal:By the mixed molten liquid for obtaining with the speed slow cooling of 10 DEG C/h of temperature to room temperature, from
Send out crystallization and obtain chloroboric acid barium seed crystal;
The seed crystal of acquisition is fixed on on seed rod seed crystal lower from crystal growing furnace top, first seed crystal is preheated 25 minutes, is made
Seed crystal carries out melt back down to mixed molten liquid surface, constant temperature 25 minutes, fast cooling to 900 DEG C of temperature;
Lowered the temperature with the speed of DEG C/day of temperature 5 again, with the rotating speed rotary seed crystal rod of 30rpm, treat crystal growth to required yardstick
Afterwards, by crystal lift-off molten surface, room temperature is down to temperature 35 DEG C/h speed, is then taken out crystal from burner hearth, you can obtain
Obtain Ba of the size for 22mm × 32mm × 20mm7B3O11Cl crystal.
Raw material barium nitrate in reaction equation can be with barium bicarbonate or brium carbonate or barium oxalate or barium hydroxide or Barium monoxide
Replace, boron oxide can be replaced by boric acid.
Embodiment 8
By reaction equation:13BaO+BaCl2+3B2O3→2Ba7B3O11Cl compounds;
By BaO, BaCl2、B2O3In molar ratio 9:1:3 are put in mortar, and mixing is simultaneously carefully ground, and is then charged into Φ 100mm
In the opening corundum crucible of × 100mm, compressed, in being put into Muffle furnace, be to slowly warm up to 750 DEG C of temperature, constant temperature 24 hours,
Crucible is taken out after cooling, now sample is more loose, then take out sample and re-grind uniformly, then be placed in crucible, in Muffle
In 980 DEG C of temperature constant temperature 48 hours again in stove, it is drawn off, is put in mortar and smashs grinding to pieces and obtain final product Ba7B3O11Cl compounds, it is right
The product carries out X-ray analyses, gained X-ray spectrogram and chloroboric acid barium Ba7B3O11The X-ray spectrogram that Cl mono-crystalline structures are obtained is
Consistent;
Then by the Ba of synthesis7B3O11Cl compounds and flux Na2O-PbO in molar ratio 1:4, mixture is carried out, wherein
Na2O is 2 with PbO mol ratios:2, in being fitted into the opening platinum crucible of Φ 80mm × 80mm, it is warming up to 970 DEG C of temperature, constant temperature 70
Hour, mixed molten liquid is obtained, then it is down to 925 DEG C of temperature;
Prepare chloroboric acid barium seed crystal:By the mixed molten liquid for obtaining with the speed slow cooling of 4.0 DEG C/h of temperature to room temperature, from
Send out crystallization and obtain chloroboric acid barium seed crystal;
The Ba that will be obtained7B3O11Cl seed crystals are fixed on seed rod seed crystal lower from crystal growing furnace top, first preheat seed crystal 8
Minute, make seed crystal carry out melt back down to mixed molten liquid surface, constant temperature 8 minutes, fast cooling to 920 DEG C of temperature;
Again with the speed slow cooling of DEG C/day of temperature 0.8, seed crystal crucible is rotated with the rotating speed of 10rpm, treat that crystal growth is arrived
After required yardstick, by crystals from molten surface, room temperature is down to temperature 5 DEG C/h speed, then takes out crystal from burner hearth,
Ba of the size for 18mm × 22mm × 15mm can be obtained7B3O11Cl crystal.
Raw material Barium monoxide in reaction equation can be with brium carbonate or barium bicarbonate or barium oxalate or barium hydroxide or barium nitrate
Replace, boron oxide can be replaced by boric acid.
Embodiment 9
By reaction equation:13Ba(OH)2+BaCl2+3B2O3→2Ba7B3O11Cl+13H2O ↑ synthesis Ba7B3O11Cl compounds:
By Ba (OH)2、BaCl2、B2O3In molar ratio 9:1:3 are put in mortar, and mixing is simultaneously carefully ground, and is then charged into Φ
In the opening corundum crucible of 100mm × 100mm, compressed, in being put into Muffle furnace, be to slowly warm up to 750 DEG C of temperature, constant temperature 24
Hour, crucible is taken out after cooling, now sample is more loose, then takes out sample and re-grinds uniformly, then is placed in crucible,
In 980 DEG C of temperature constant temperature 48 hours again in Muffle furnace, it is drawn off, is put in mortar and smashs grinding to pieces and obtain final product Ba7B3O11Cl chemical combination
Thing, X-ray analyses, gained X-ray spectrogram and chloroboric acid barium Ba are carried out to the product7B3O11The X-ray that Cl mono-crystalline structures are obtained
Spectrogram is consistent;
Then by the Ba of synthesis7B3O11Cl compounds and flux H3BO3- PbO in molar ratio 1:4, carry out mixture, H3BO
It is 2 with PbO mol ratios:1, in being fitted into the opening platinum crucible of Φ 80mm × 80mm, it is warming up to 830 DEG C of temperature, constant temperature 45 hours,
Mixed molten liquid is obtained, then is down to 820 DEG C of temperature;
Prepare chloroboric acid barium seed crystal:By the mixed molten liquid for obtaining with the speed slow cooling of 6.5 DEG C/h of temperature to room temperature, from
Send out crystallization and obtain chloroboric acid barium seed crystal;
The Ba that will be obtained7B3O11Cl seed crystals are fixed on seed rod seed crystal lower from crystal growing furnace top, first preheat seed crystal
15 minutes, seed crystal is set to carry out melt back down to mixed molten liquid surface, constant temperature 15 minutes, fast cooling to 815 DEG C of saturation temperature;
Again with the speed slow cooling of DEG C/day of temperature 2, with the rotating speed rotary seed crystal rod of 60rpm, treat crystal growth to required
After yardstick, by crystals from molten surface, room temperature is down to temperature 80 DEG C/h speed, is then taken out crystal from burner hearth, i.e.,
The Ba that size is 24mm × 22mm × 15mm can be obtained7B3O11Cl crystal.
Raw material barium hydroxide in reaction equation can be with brium carbonate or barium bicarbonate or barium oxalate or barium nitrate or Barium monoxide
Replace, boron oxide can be replaced by boric acid.
Embodiment 10
By reaction equation:13Ba(HCO3)2+BaCl2+3B2O3→2Ba7B3O11Cl+26CO2↑+13H2O ↑ synthesis Ba7B3O11Cl
Compound:
By Ba (HCO3)2、BaCl2、B2O3In molar ratio 9:1:3 are put in mortar, and mixing is simultaneously carefully ground, and is then charged into Φ
In the opening corundum crucible of 100mm × 100mm, compressed, in being put into Muffle furnace, be to slowly warm up to 750 DEG C of temperature, constant temperature 24
Hour, crucible is taken out after cooling, now sample is more loose, then takes out sample and re-grinds uniformly, then is placed in crucible,
In 980 DEG C of temperature constant temperature 48 hours again in Muffle furnace, it is drawn off, is put in mortar and smashs grinding to pieces and obtain final product Ba7B3O11Cl chemical combination
Thing, X-ray analyses, gained X-ray spectrogram and chloroboric acid barium Ba are carried out to the product7B3O11The X-ray that Cl mono-crystalline structures are obtained
Spectrogram is consistent;、
By the Ba of synthesis7B3O11Cl compounds and flux NaCl-PbO in molar ratio 3:2 carry out mixture, wherein NaCl with
PbO mol ratios are 2:1, in being fitted into the opening platinum crucible of Φ 80mm × 80mm, 1100 DEG C of temperature is warming up to, constant temperature is obtained for 5 hours
Mixed molten liquid, then it is down to 950 DEG C of temperature;
Prepare chloroboric acid barium seed crystal:By the mixed molten liquid for obtaining with the speed slow cooling of 4.0 DEG C/h of temperature to room temperature, from
Send out crystallization and obtain chloroboric acid barium seed crystal;
The Ba that will be obtained7B3O11Cl seed crystals are fixed on seed rod seed crystal lower from crystal growing furnace top, first preheat seed crystal
20 minutes, seed crystal is set to carry out melt back down to mixed molten liquid surface, constant temperature 25 minutes, fast cooling to 945 DEG C of temperature;
Then lowered the temperature with the speed of DEG C/day of temperature 3, with the rotating speed rotary seed crystal rod of 50rpm, treat crystal growth to required chi
After degree, by crystals from molten surface, room temperature is down to temperature 70 C/h speed, then takes out crystal from burner hearth, you can
Acquisition size is the Ba of 22mm × 21mm × 16mm7B3O11Cl crystal.
Oxide spinel hydrogen barium in reaction equation can be with brium carbonate or barium hydroxide or barium oxalate or barium nitrate or Barium monoxide
Replace, boron oxide can be replaced by boric acid;
Embodiment 11
By reaction equation:13BaC2O4+BaCl2+3B2O3→2Ba7B3O11Cl+13CO2↑+13CO ↑ synthesis Ba7B3O11Cl chemical combination
Thing:
By BaC2O4、BaCl2、B2O3In molar ratio 9:1:3 are put in mortar, and mixing is simultaneously carefully ground, and is then charged into Φ
In the opening corundum crucible of 100mm × 100mm, compressed, in being put into Muffle furnace, be to slowly warm up to 750 DEG C of temperature, constant temperature 24
Hour, crucible is taken out after cooling, now sample is more loose, then takes out sample and re-grinds uniformly, then is placed in crucible,
In 980 DEG C of temperature constant temperature 48 hours again in Muffle furnace, it is drawn off, is put in mortar and smashs grinding to pieces and obtain final product Ba7B3O11Cl chemical combination
Thing, X-ray analyses, gained X-ray spectrogram and chloroboric acid barium Ba are carried out to the product7B3O11The X-ray that Cl mono-crystalline structures are obtained
Spectrogram is consistent;、
By the Ba of synthesis7B3O11Cl compounds and flux H3BO3- PbO in molar ratio 1:3 carry out mixture, wherein H3BO3With
PbO mol ratios are 5:1, in being fitted into the opening platinum crucible of Φ 80mm × 80mm, 1000 DEG C of temperature is warming up to, constant temperature is obtained for 50 hours
Mixed molten liquid, then it is down to 920 DEG C of temperature;
Prepare chloroboric acid barium seed crystal:By the mixed molten liquid for obtaining with the speed slow cooling of 10 DEG C/h of temperature to room temperature, from
Send out crystallization and obtain chloroboric acid barium seed crystal;
The Ba that will be obtained7B3O11Cl seed crystals are fixed on seed rod seed crystal lower from crystal growing furnace top, first preheat seed crystal
20 minutes, seed crystal is set to carry out melt back down to mixed molten liquid surface, constant temperature 25 minutes is cooled to 915 DEG C of saturation temperature;
Then lowered the temperature with the speed of DEG C/day of temperature 2, with the rotating speed rotary seed crystal rod of 28rpm, treat crystal growth to required chi
After degree, by crystals from molten surface, room temperature is down to temperature 25 DEG C/h speed, then takes out crystal from burner hearth, you can
Acquisition size is the Ba of 30mm × 22mm × 15mm7B3O11Cl crystal.
Raw material barium oxalate in reaction equation can be with brium carbonate or barium hydroxide or barium bicarbonate or barium nitrate or Barium monoxide
Replace, boron oxide can be replaced by boric acid;
Embodiment 12
By the arbitrary Ba of embodiment 1-11 gained7B3O11Cl crystal is by the direction processing one block size 5mm × 5mm that matches
The frequency doubling device of × 6mm, by being placed on 3 position accompanying drawing 2 Suo Shi, at room temperature, with tune Q Nd:YAG laser makees light source,
Incident wavelength is 1064nm, by tune Q Nd:YAG laser 1 sends the infrared beam 2 that wavelength is 1064nm and injects Ba7B3O11Cl
Monocrystalline 3, produces green frequency doubled light of the wavelength for 532nm, and output intensity is 0.5 times of equal conditions KDP, and outgoing beam 4 contains
Wavelength is the infrared light of 1064nm and the green glow of 532nm, and the green laser that wavelength is 532nm is obtained after filtered 5 elimination.
Claims (5)
1. a kind of compound chloroboric acid barium, it is characterised in that the chemical formula of the compound is Ba7B3O11Cl, molecular weight 1205.26,
Compound is synthesized using solid reaction process.
2. a kind of compound chloroboric acid barium nonlinear optical crystal, it is characterised in that the chemical formula of the crystal is Ba7B3O11Cl, point
Son amount 1205.26, not with symmetrical centre, belongs to hexagonal crystal system, space group P63Mc, cell parameter is a=11.2266 (17),
C=7.214 (2), Z=2, V=787.4 (3)3。
3. the preparation method of compound chloroboric acid barium nonlinear optical crystal according to claim 2, it is characterised in that adopt
Synthesize compound and high temperature solution method growth crystal with solid reaction process, concrete operations follow these steps to carry out:
A, by containing barium compound be brium carbonate, barium nitrate, Barium monoxide, barium hydroxide, barium bicarbonate or barium oxalate, chlorine-containing compound
It is H for barium chloride and boron-containing compound3BO3Or B2O3In molar ratio 9:1:3-6 is weighed and is put in mortar, and mixing is simultaneously carefully ground,
In being then charged into the opening corundum crucible of Φ 100mm × 100mm, in being put into Muffle furnace, 650 DEG C are to slowly warm up to, constant temperature 24 is little
When, it is cooled to room temperature, take out after Jing grinds for second and be put in Muffle furnace, then it is warming up to 750 DEG C, and constant temperature 24 hours, cooling
To room temperature, take out Jing after third time is ground and be put in Muffle furnace, then be warming up to 900 DEG C, constant temperature 48 hours takes out ground obtaining
Chloroboric acid barium compound single-phase polycrystalline powder, then X-ray analyses are carried out to the product, gained X-ray spectrogram and chloroboric acid barium
Ba7B3O11The X-ray spectrogram that Cl mono-crystalline structures are obtained is consistent;
B, the single-phase polycrystalline powder that step a is obtained and flux are NaCl-H3BO3、H3BO3-Na2O、Na2O-PbO、LiCl-
PbO, NaCl-PbO or H3BO3- PbO mix homogeneously, with the heating rate of temperature 1-30 DEG C/h temperature 650-1200 DEG C is heated to,
Constant temperature 5-80 hours, obtain mixed molten liquid, then are cooled to temperature 610-1000 DEG C, wherein chloroboric acid barium compound single-phase polycrystalline powder
End is 1 with the mol ratio of flux:1-12;
Or directly by containing barium compound be brium carbonate, barium nitrate, Barium monoxide, barium hydroxide, barium bicarbonate or barium oxalate, chloride containing
Compound is barium chloride and boron-containing compound is H3BO3Or B2O3It is NaCl-H with flux3BO3、H3BO3-Na2O、Na2O-PbO、
LiCl-PbO, NaCl-PbO or H3BO3- PbO mix homogeneously, with the heating rate of temperature 1-30 DEG C/h temperature 650- is heated to
1200 DEG C, constant temperature 5-80 hours obtain mixed molten liquid, then are cooled to temperature 610-1000 DEG C, wherein baric, chloride and containing boronation
Compound is 9 with the mol ratio of flux:1:6:1-12;
C, prepare chloroboric acid barium seed crystal:The mixed molten liquid that step b is obtained is slowly dropped to room with the speed of temperature 0.5-10 DEG C/h
Temperature, spontaneous crystallization obtains chloroboric acid barium seed crystal;
D, the crucible for filling mixed molten liquid obtained in step b is inserted in crystal growing furnace, the seed crystal that step c is obtained is fixed on
On seed rod, from the lower seed crystal in crystal growing furnace top, seed crystal 5-60 minutes are first preheated, by seed crystal down to contact mixed molten liquid liquid table
Face carries out melt back down in mixed molten liquid, constant temperature 5-60 minutes, with the speed of temperature 1-60 DEG C/h temperature 750-945 is down to
℃;
E, again with temperature 0.1-5 DEG C/day speed slow cooling, with the growth that 0-60rpm rotating speeds rotary seed crystal rod carries out crystal,
After crystal growth to required yardstick, by crystal lift-off mixed molten liquid surface, and room temperature is down to temperature 1-80 DEG C/h speed, so
Crystal is taken out from burner hearth afterwards, you can obtain chloroboric acid barium nonlinear optical crystal.
4. the preparation method of compound chloroboric acid barium nonlinear optical crystal according to claim 3, it is characterised in that step
Rapid b flux NaCl-H3BO3NaCl and H in system3BO3Mol ratio be 1-5:3-6;LiCl-PbO or NaCl-PbO systems
Middle chloride is 1-5 with the mol ratio of lead oxide:1-6;H3BO3- PbO or H3BO3-Na2O systems mesoboric acid rubs with oxide
You are than being 2-5:1-5;Na2Sodium oxide and the mol ratio of lead oxide are 1-5 in O-PbO systems:0.1-6.
5. chloroboric acid barium nonlinear optical crystal according to claim 2 prepare times frequency generator, upper frequency transducer,
The purposes of lower frequency transducer or optical parametric oscillator.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310591017.4A CN104651933B (en) | 2013-11-21 | 2013-11-21 | Chlorine barium borate, chlorine barium borate nonlinear optical crystal, and preparation method and uses of chlorine barium borate nonlinear optical crystal |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310591017.4A CN104651933B (en) | 2013-11-21 | 2013-11-21 | Chlorine barium borate, chlorine barium borate nonlinear optical crystal, and preparation method and uses of chlorine barium borate nonlinear optical crystal |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104651933A CN104651933A (en) | 2015-05-27 |
CN104651933B true CN104651933B (en) | 2017-04-19 |
Family
ID=53243555
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310591017.4A Active CN104651933B (en) | 2013-11-21 | 2013-11-21 | Chlorine barium borate, chlorine barium borate nonlinear optical crystal, and preparation method and uses of chlorine barium borate nonlinear optical crystal |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104651933B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105332054B (en) * | 2014-08-08 | 2018-01-02 | 中国科学院新疆理化技术研究所 | Compound sodium chloroborate and sodium chloroborate optical crystal and preparation method and purposes |
CN106544731A (en) | 2015-09-19 | 2017-03-29 | 中国科学院新疆理化技术研究所 | Lead chlorate infrared nonlinear optical crystal and preparation method and purposes |
CN108957596B (en) * | 2018-03-09 | 2020-10-30 | 中国科学院福建物质结构研究所 | Deep ultraviolet window device comprising boracite crystals |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101914809A (en) * | 2010-08-11 | 2010-12-15 | 中国科学院新疆理化技术研究所 | Nonlinear optical crystal of potassium borate chloride compound and preparation method as well as application thereof |
CN101984149A (en) * | 2010-11-22 | 2011-03-09 | 中国科学院新疆理化技术研究所 | Method for preparing large chlorine barium borate nonlinear optic crystal and application thereof |
CN102337586A (en) * | 2010-07-20 | 2012-02-01 | 中国科学院新疆理化技术研究所 | Compound barium borofluoride nonlinear optical crystal as well as preparation method and purposes thereof |
CN102978702A (en) * | 2011-09-02 | 2013-03-20 | 中国科学院新疆理化技术研究所 | Compound barium borofluoride, barium borofluoride non-linear optical crystal, and preparation method and use of the barium borofluoride non-linear optical crystal |
CN103088423A (en) * | 2011-11-01 | 2013-05-08 | 中国科学院新疆理化技术研究所 | Compound barium boron oxyfluoride, barium boron oxyfluoride nonlinear optical crystal, and preparation methods and applications thereof |
CN103359755A (en) * | 2012-04-09 | 2013-10-23 | 中国科学院新疆理化技术研究所 | Compound pentabarium monofluortriborate and nonlinear optical crystals of pentabarium monofluortriborate, and preparation method and use thereof |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0297490A (en) * | 1988-09-30 | 1990-04-10 | Toshiba Corp | Production of srb2o4 single crystal |
JPH03279298A (en) * | 1990-03-29 | 1991-12-10 | Osamu Shimomura | Growth of beta-bab2o4 single crystal using nacl as flux |
WO2008034283A1 (en) * | 2006-09-15 | 2008-03-27 | Technical Institute Of Physics And Chemistry Chinese Academy Of Sciences | Beryllium borate fluoride salt nonlinear optical crystal, its growth method and uses |
-
2013
- 2013-11-21 CN CN201310591017.4A patent/CN104651933B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102337586A (en) * | 2010-07-20 | 2012-02-01 | 中国科学院新疆理化技术研究所 | Compound barium borofluoride nonlinear optical crystal as well as preparation method and purposes thereof |
CN101914809A (en) * | 2010-08-11 | 2010-12-15 | 中国科学院新疆理化技术研究所 | Nonlinear optical crystal of potassium borate chloride compound and preparation method as well as application thereof |
CN101984149A (en) * | 2010-11-22 | 2011-03-09 | 中国科学院新疆理化技术研究所 | Method for preparing large chlorine barium borate nonlinear optic crystal and application thereof |
CN102978702A (en) * | 2011-09-02 | 2013-03-20 | 中国科学院新疆理化技术研究所 | Compound barium borofluoride, barium borofluoride non-linear optical crystal, and preparation method and use of the barium borofluoride non-linear optical crystal |
CN103088423A (en) * | 2011-11-01 | 2013-05-08 | 中国科学院新疆理化技术研究所 | Compound barium boron oxyfluoride, barium boron oxyfluoride nonlinear optical crystal, and preparation methods and applications thereof |
CN103359755A (en) * | 2012-04-09 | 2013-10-23 | 中国科学院新疆理化技术研究所 | Compound pentabarium monofluortriborate and nonlinear optical crystals of pentabarium monofluortriborate, and preparation method and use thereof |
Non-Patent Citations (2)
Title |
---|
Crystal structures of two new Ba borates pentaborate,Ba2[B5O9]Cl·0.5H2O and Ba2[B5O8(OH)2](OH);O. Ferro et al.;《Journal of Alloys and Compounds》;20000510;第305卷(第1-2期);63-71 * |
Phase formation in the BaB2O4–BaF2–BaO system and new non-centrosymmetric solid-solution series Ba7(BO3)4-xF2+3x;T. B. Bekker et al.;《CrystEngComm》;20120806;第14卷;6910-6915 * |
Also Published As
Publication number | Publication date |
---|---|
CN104651933A (en) | 2015-05-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102337586B (en) | Compound barium borofluoride nonlinear optical crystal as well as preparation method and purposes thereof | |
CN102127811B (en) | Lead fluoroborate nonlinear optical crystal as well as preparation method and application thereof | |
CN103361725B (en) | Compound chloroboric acid lead barium and chloroboric acid lead barium nonlinear optical crystal and preparation method and purposes | |
CN102978702B (en) | Compound barium borofluoride, barium borofluoride non-linear optical crystal, and preparation method and use of the barium borofluoride non-linear optical crystal | |
CN107699948B (en) | Serial composition metal RE borate and composition metal RE borate nonlinear optical crystal and preparation method and purposes | |
CN101311370A (en) | Large-sized bismuth zinc borate nonlinear optical crystal, preparation method and use | |
CN106283192B (en) | Compound lead barium zinc boron oxygen and lead barium zinc boron oxygen nonlinear optical crystal and preparation method and purposes | |
CN103741217B (en) | Yttrium borate sodium, yttrium borate sodium nonlinear optical crystal and preparation method and purposes | |
CN104213194B (en) | Chlorine borosilicic acid barium and chlorine borosilicic acid barium nonlinear optical crystal and preparation method and purposes | |
CN103361726B (en) | Compound sodium phosphate lithium and sodium phosphate lithium non-linear optic crystal and preparation method and purposes | |
CN101984151B (en) | Di lithium tetra borate rubidium nonlinear optic crystal, preparation method and application thereof | |
CN103803572B (en) | Compound lithium-fluoroborate calcium and lithium-fluoroborate calcium non-linear optical crystal and preparation method and purposes | |
CN106868587A (en) | Lithium rubidium barium aluminium boroxide fluorine and lithium rubidium barium aluminium boroxide fluorine nonlinear optical crystal and preparation method and purposes | |
CN106868590B (en) | Compound barium fluoborate magnesium and barium fluoborate magnesium nonlinear optical crystal and preparation method and purposes | |
CN105986318B (en) | Boronic acid compound barium caesium and barium borate caesium nonlinear optical crystal and preparation method and purposes | |
CN104651933B (en) | Chlorine barium borate, chlorine barium borate nonlinear optical crystal, and preparation method and uses of chlorine barium borate nonlinear optical crystal | |
CN103173859A (en) | Cadmium sodium borophosphate compound, cadmium sodium borophosphate nonlinear optical crystal, preparation methods of compound and crystal, and use of crystal | |
CN101974783B (en) | Compound cesium lithium borate (CLBO) nonlinear optical crystal, preparation method and application thereof | |
CN105502329B (en) | RbNaMgP2O7Compound, RbNaMgP2O7Nonlinear optical crystal and its preparation method and purposes | |
CN103359755B (en) | Compound pentabarium monofluortriborate and nonlinear optical crystals of pentabarium monofluortriborate, and preparation method and use thereof | |
CN104746140B (en) | Compound potassium sodium boron oxygen bromine nonlinear optical crystal and preparation method and purposes | |
CN107217301B (en) | Compound lithium fluoroborate potassium and lithium fluoroborate nonlinear optical crystal of potassium and preparation method and purposes | |
CN106884204A (en) | Lithium potassium strontium aluminium boroxide fluorine and lithium potassium strontium aluminium boroxide fluorine nonlinear optical crystal and preparation method and purposes | |
CN1122732C (en) | Non-linear optical crystal of magnesium zinc bromophosphate and its preparing process and application | |
CN105316763B (en) | Compound fluoboric acid cadmium lead and fluoboric acid cadmium lead nonlinear optical crystal and preparation method and purposes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |