CN109680332A - Compound tin boron oxygen chlorine and tin boron oxygen chlorine nonlinear optical crystal and preparation method and purposes - Google Patents
Compound tin boron oxygen chlorine and tin boron oxygen chlorine nonlinear optical crystal and preparation method and purposes Download PDFInfo
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- CN109680332A CN109680332A CN201910166628.1A CN201910166628A CN109680332A CN 109680332 A CN109680332 A CN 109680332A CN 201910166628 A CN201910166628 A CN 201910166628A CN 109680332 A CN109680332 A CN 109680332A
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- 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
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- 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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/02—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method without using solvents
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- 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
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
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- 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
- C30B17/00—Single-crystal growth onto a seed which remains in the melt during growth, e.g. Nacken-Kyropoulos method
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
Abstract
The present invention provides a kind of compound tin boron oxygen chlorine and tin boron oxygen chlorine nonlinear optical crystal and preparation method and purposes, and the chemical formula of the compound is Sn2B5O9Cl, molecular weight 470.70 are made of solid-phase synthesis or Vacuum Package method；The chemical formula of the compound of the crystal is Sn2B5O9Cl, molecular weight 470.70 belong to rhombic system, and space group isPnn2, cell parameter isa=11.281 (3),b=11.331 (3),c=6.5573 (19),α=90 °,β=90 °,γ=90 °, unit-cell volume is 838.2 (4)3, the frequency-doubled effect of crystal is about KH2PO4(KDP) 0.5 times, ultraviolet cut-on side is lower than 350nm, using melt method, high temperature solution method, Vacuum Package method, hydro-thermal method or solution at room temperature method grow crystal, the chemical stability of the crystal is good, can be used as short wavelength's nonlinear optical crystal and is applied in all solid state laser.
Description
Technical field
The present invention relates to a kind of compound tin boron oxygen chlorine Sn2B5O9Cl and tin boron oxygen chlorine Sn2B5O9Cl nonlinear optical crystal
And preparation method and purposes.
Background technique
Short wavelength's nonlinear optical crystal can be turned the laser of the wave bands such as near-infrared, visible using its frequency conversion property
It changes short wavelength laser into, there is significant application value in fields such as medical treatment, communication, scientific researches.It is well known that practical at present
Short wavelength's nonlinear optical crystal be China scientist invention KBe2BO3F2(KBBF) crystal, BaB2O4(BBO) and LiB3O5
(LBO), however these crystal have the defects of growing large-size crystal is difficult, and birefringence is small, limit it to a certain extent
Using.Therefore, novel short wavelength's non-linear optical crystal material that preparation synthesizes excellent combination property is of great significance and reality
With value.
The present invention in research before this, have compound chloroboric acid lead barium and chloroboric acid lead barium nonlinear optical crystal and
Preparation method and purposes (number of patent application CN201210081872), compound chloroboric acid nonlinear optical crystal of potassium and preparation side
Method and purposes (number of patent application CN201010250911), chloroboric acid barium and chloroboric acid barium nonlinear optical crystal and preparation method
With purposes (number of patent application CN201310591017), compound sodium chloroborate and sodium chloroborate optical crystal and preparation method and
Purposes (CN201410390210) and compound chloroboric acid rubidium sodium and chloroboric acid rubidium sodium optical crystal and preparation method and purposes
(number of patent application CN201410390209) five related patents.Present invention main distinction of five patents with more than is, this
The invention compound Sn2B5O9Cl space group is Pnn2, belongs to rhombic system.In addition, habit, growth technique are crucial
Parameter, crystal linear and nonlinear optical property etc. are different from the first six person.
Summary of the invention
Present invention aims at provide a kind of compound tin boron oxygen chlorine, the chemical formula of the compound is Sn2B5O9Cl, molecule
Amount is 470.70, is prepared using solid reaction process or Vacuum Package method.
It is a further object of the invention to provide tin boron oxygen chlorine Sn2B5O9Cl nonlinear optical crystal, the change of the crystal
Formula is Sn2B5O9Cl, molecular weight 470.70.Belong to rhombic system, space group Pnn2, cell parameter is α=90 °, β=90 °, γ=90 °, unit-cell volume
For
Further object of the present invention is, provides tin boron oxygen chlorine Sn2B5O9The preparation method of Cl nonlinear optical crystal, is adopted
With melt method, high temperature solution method, Vacuum Package method, hydro-thermal method or solution at room temperature method grow crystal.
Another object of the present invention is, provides tin boron oxygen chlorine Sn2B5O9The purposes of Cl nonlinear optical crystal.
A kind of compound tin boron oxygen chlorine of the present invention, the chemical formula of the compound are Sn2B5O9Cl, molecular weight are
470.70, it is made of solid-phase synthesis or Vacuum Package method.
The preparation method of the compound tin boron oxygen chlorine is prepared using solid-phase synthesis or Vacuum Package method, specific to grasp
It follows these steps to carry out:
The solid-phase synthesis prepare compound tin boron oxygen chlorine:
Sn compound, boride alloy and compound containing Cl will be contained to be uniformly mixed at Sn: B: Cl=2: 5: 1 in molar ratio, be packed into
Platinum crucible is placed in Muffle furnace in a vacuum or inert atmosphere, is warming up to 400-700 DEG C, and constant temperature 24-120 hours is to get arriving
Compound Sn2B5O9Cl, the SnO of compound containing Sn, SnCl2Or SnB4O7；Boride alloy H3BO3、B2O3Or SnB4O7；Containing Cl
For compound SnCl2；
The Vacuum Package method prepare compound tin boron oxygen chlorine:
Sn compound, boride alloy and compound containing Cl will be contained to be uniformly mixed at Sn: B: Cl=2: 5: 1 in molar ratio, be packed into
In quartz ampoule, quartz ampoule is vacuumized, vacuum degree reaches 1 × 10-3Pa, elevated-temperature seal are placed in Muffle furnace, with 5-10 DEG C/h
Rate be warming up to 400-700 DEG C, constant temperature 24-120 hours is to get arriving compound Sn2B5O9Cl, wherein the compound containing Sn
For SnO, SnCl2Or SnB4O7；Boride alloy is H3BO3、B2O3Or SnB4O7；It is compound SnCl containing Cl2。
A kind of tin boron oxygen chlorine nonlinear optical crystal, the chemical formula of the crystal are Sn2B5O8Cl, molecular weight 470.70, belongs to
Rhombic system, space group Pnn2, cell parameter areα
=90 °, β=90 °, γ=90 °, unit-cell volume is
The preparation method of tin boron oxygen chlorine nonlinear optical crystal, using melt method, high temperature solution method, Vacuum Package method, water
Thermal method or solution at room temperature method grow crystal；
The concrete operations of the melt method for growing tin boron oxygen chlorine nonlinear optical crystal follow these steps to carry out:
A, Sn compound, boride alloy and compound containing Cl will be contained to be uniformly mixed at Sn: B: Cl=2: 5: 1 in molar ratio, dress
Enter platinum crucible, be placed in Muffle furnace in a vacuum or inert atmosphere, be warming up to 400-600 DEG C, constant temperature 24-120 hours to get
To Sn2B5O9Cl polycrystal powder, wherein the compound containing Sn is SnO, SnCl2Or SnB4O7；Boride alloy is H3BO3、B2O3
Or SnB4O7；It is compound SnCl containing Cl2；
B, the Sn for obtaining step a2B5O8Cl polycrystal powder is packed into platinum crucible, is placed in Muffle furnace in vacuum or inertia
Under atmosphere, it is warming up to 600-800 DEG C, constant temperature 10-120 hours, obtains blend melt；
C, the blend melt that step b is obtained is slowly dropped to 300 DEG C with the rate of 0.1-2 DEG C/h, then with 5-10 DEG C/h's
Rate fast cooling obtains Sn to room temperature2B5O9Cl seed crystal；
D, crystal is grown in blend melt using czochralski method: the obtained seed crystal of step c is fixed on seed rod, from step
Seed crystal under the top of blend melt made from rapid b was turned by the crystalline substance that crystal growth controller applies 2-20rpm, with 1-10mm/ days
Speed lift seed crystal, while with the rate of 0.1-10 DEG C/h cooling, after crystal growth stopping after to get arrive Sn2B5O8Cl is non-thread
Property optical crystal；
Or crystal is grown in blend melt with kyropoulos: the obtained seed crystal of step c being fixed on seed rod, from step
Seed crystal under the top of blend melt made from b is cooled down with the rate of 0.1-10 DEG C/h of temperature, makes crystal growth 5-15 hours, is delayed
It is slow to promote crystal but do not depart from liquid level continued growth, it so repeats, arrives Sn after crystal growth stopping2B5O9Cl is non-linear
Optical crystal；
Or crystal is grown in blend melt with Bridgman-Stockbarger method: the obtained seed crystal of step c being placed on crucible bottom, then will
The Sn of step a preparation2B5O9Cl polycrystalline is put into crucible, then seals platinum crucible, and growth furnace temperature is risen to 550-750
DEG C, constant temperature 10-120 hours, adjustment bushing position kept seed crystal micro- molten, crucible was then reduced with 1-10mm/ days speed, meanwhile,
It keeps growth temperature constant, or is down to 350 DEG C, after to be grown with prestissimo with the rate of temperature fall of 3 DEG C/h, then with 5-10
DEG C/rate of h is down to room temperature quickly to get to Sn2B5O9Cl nonlinear optical crystal；
The concrete operations of the high temperature solution method growth tin boron oxygen chlorine nonlinear optical crystal follow these steps to carry out:
A, Sn compound, boride alloy and compound containing Cl will be contained to be uniformly mixed at Sn: B: Cl=2: 5: 1 in molar ratio, dress
Enter platinum crucible, be placed in Muffle furnace in a vacuum or inert atmosphere, be warming up to 400-600 DEG C, constant temperature 24-120 hours to get
To Sn2B5O9Cl polycrystal powder, wherein the compound containing Sn is SnO, SnCl2Or SnB4O7；Boride alloy is H3BO3、B2O3
Or SnB4O7；It is compound SnCl containing Cl2；
B, the Sn for obtaining step a2B5O9Cl polycrystal powder 1: 0.1-6 is uniformly mixed in molar ratio with cosolvent, is reloaded into
In platinum crucible, it is warming up to 500-800 DEG C, constant temperature 5-120 hours, obtains mixed molten liquid；Wherein the cosolvent is SnCl2、
H3BO3Or B2O3；
C, it prepares seed crystal: the obtained mixed molten liquid of step b being placed in single crystal growing furnace, is slowly dropped with the rate of 0.1-2 DEG C/h
Sn is obtained to room temperature to 350 DEG C, then with the rate fast cooling of 5-10 DEG C/h2B5O9Cl seed crystal；
D, grow crystal: the obtained seed crystal of step c be fixed on seed rod, the mixed molten liquid made from the step b it is upper
The lower seed crystal in side, is turned by the crystalline substance that crystal growth controller applies 2-20rpm, is cooled down with the rate of 0.1-3 DEG C/h, to crystal growth
After stopping to get arrive Sn2B5O9Cl nonlinear optical crystal；
The concrete operations of the Vacuum Package method growth tin boron oxygen chlorine nonlinear optical crystal follow these steps to carry out:
A, Sn compound, boride alloy and compound containing Cl will be contained to be uniformly mixed at Sn: B: Cl=2: 5: 1 in molar ratio, dress
Enter platinum crucible, be placed in Muffle furnace in a vacuum or inert atmosphere, be warming up to 400-600 DEG C, constant temperature 24-120 hours to get
To Sn2B5O9Cl polycrystal powder, wherein the compound containing Sn is SnO, SnCl2Or SnB4O7；Boride alloy is H3BO3、B2O3
Or SnB4O7；It is compound SnCl containing Cl2；
B, the Sn for obtaining step a2B5O9Cl polycrystal powder 0-1: 0.1-6 is uniformly mixed in molar ratio with cosolvent, is packed into
In quartz ampoule, elevated-temperature seal is placed in Muffle furnace, is warming up to 500-800 DEG C, and constant temperature 5-120 hours, then with 0.1-3 DEG C/h
Rate be cooled to 350 DEG C, then with the rate fast cooling of 5-10 DEG C/h to room temperature to get arriving Sn2B5O9Cl non-linear optical crystal
Body, wherein the cosolvent is SnCl2、H3BO3Or B2O3；
The concrete operations of the Hydrothermal Growth tin boron oxygen chlorine nonlinear optical crystal follow these steps to carry out:
A, Sn compound, boride alloy and compound containing Cl will be contained to be uniformly mixed at Sn: B: Cl=2: 5: 1 in molar ratio, dress
Enter platinum crucible, be placed in Muffle furnace, in a vacuum or inert atmosphere, is warming up to 400-600 DEG C, constant temperature 24-120 hours, i.e.,
Obtain Sn2B5O9Cl polycrystal powder, wherein the compound containing Sn is SnO, SnCl2Or SnB4O7；Boride alloy is H3BO3、
B2O3Or SnB4O7；Compound containing Cl is SnCl2；
B, the SnB for obtaining step a4O6It is dissolved in Cl polycrystal powder merging deionized water, by the mixture of endless fully dissolved
In temperature 60 C ultrasonication, dissolution is mixed them thoroughly, with HCl and NH3·H2It is 8-11 that O, which adjusts pH value, obtains mixing molten
Liquid；
C, the obtained mixed solution of step b is transferred in the autoclave that clean, free of contamination volume is 100mL
In lining, and by reaction kettle screwing hermetic；
D, autoclave is placed in insulating box, is warming up to 150-350 DEG C, constant temperature 5-8 days, then with 5-20 DEG C/day
Rate of temperature fall be down to room temperature to get to Sn2B5O9Cl nonlinear optical crystal；
The concrete operations of the solution at room temperature method growth tin boron oxygen chlorine nonlinear optical crystal follow these steps to carry out:
A, Sn compound, boride alloy and compound containing Cl will be contained to be uniformly mixed at Sn: B: Cl=2: 5: 1 in molar ratio, dress
Enter platinum crucible, be placed in Muffle furnace in a vacuum or inert atmosphere, be warming up to 400-600 DEG C, constant temperature 24-120 hours to get
To Sn2B5O9Cl polycrystal powder, wherein the compound containing Sn is SnO, SnCl2Or SnB4O7；Boride alloy is H3BO3、B2O3
Or SnB4O7；It is compound SnCl containing Cl2；
B, the Sn for obtaining step a2B5O9Cl polycrystal powder is put into the glass container of wash clean, and 20-100mL is added and goes
Ionized water, then ultrasonication makes to be sufficiently mixed dissolution, with HCl and NH3·H2It is 8-11 that O, which adjusts pH value, is filtered with filter paper
To mixed solution；
C, the obtained mixed solution of step b is placed in clean glass container, is sealed with pan paper, be placed on without shake,
It is pollution-free, without in cross-ventilated static environment, evaporation rate of several apertures to adjust water in aqueous solution is pricked into sealing,
Stand 5-20 days at room temperature；
D, crystal grain is grown in container bottom to the solution in step c, until the no longer significant change of crystal grain size,
Obtain seed crystal；
E, the preferable seed crystal of quality in step d is selected, is hung in mixed solution made from step b, at room temperature
Growth is stood 10-30 days to get Sn is arrived2B5O9Cl nonlinear optical crystal.
The tin boron oxygen chlorine nonlinear optical crystal the fundamental frequency light for preparing the 1064nm that Nd:YAG laser is exported into
The purposes of 2 frequency multiplication of row, 3 multiplied frequency harmonic light outputs.
Purposes of the tin boron oxygen chlorine nonlinear optical crystal in short wavelength's frequency multiplication light output that preparation generates 355nm.
Tin boron oxygen chlorine nonlinear optical crystal is in preparation times frequency generator, up or down frequency converter or optical parametric oscillator
In purposes.
The preparation method of tin boron oxygen chlorine nonlinear optical crystal of the present invention, container used is platinum during the preparation process
Golden crucible, iridium crucible, ceramic crucible, quartz ampoule, conical flask, beaker, liner is polytetrafluoroethyllining lining or platinum casing is housed
Stainless steel inner lining water heating kettle.When container is quartz ampoule, needs to vacuumize before sealing, raw material in reaction process is avoided to wave
Hair bursts quartz ampoule., must be first clean by cleaning container with acid when container is conical flask or beaker, then with deionized water rinse,
It dries.
The preparation method of tin boron oxygen chlorine nonlinear optical crystal of the present invention, during the preparation process resistance furnace used
For Muffle furnace or drying box.
Using the preparation method of tin boron oxygen chlorine nonlinear optical crystal of the present invention, large scale is used by this method
Crucible or container, and extend the growth cycle of crystal, then it can get corresponding large-sized Sn2B5O9Cl nonlinear optical crystal,
The Sn2B5O9The growing crystals of Cl nonlinear optical crystal are easily grown up transparent no package, have the speed of growth fast, at low cost, are held
The advantages that easily obtaining large-size crystals.
Using the preparation method of tin boron oxygen chlorine nonlinear optical crystal of the present invention, the large scale Sn of acquisition2B5O9Cl
Nonlinear optical crystal orients crystal blank according to the crystallography data of crystal, by required angle, thickness and sectional dimension
Sliced crystal polishes the light pass surface of crystal, can be used as device for non-linear optical use, the Sn2B5O9Cl non-linear optical crystal
The advantages that body has transmission region up to 300nm or so, and physical and chemical performance is stablized, is not easy to deliquesce, easy to process and preservation.
Detailed description of the invention
Fig. 1 is the compounds of this invention Sn2B5O9The powder X-ray RD spectrogram of Cl；
Fig. 2 is Sn of the present invention2B5O9The structure chart of Cl crystal；
Fig. 3 is Sn of the present invention2B5O9The working principle diagram of the device for non-linear optical of Cl crystal production, wherein 1 is laser
Device, 2 is issue light beam, and 3 be Sn2B5O9Cl crystal, 4 be outgoing beam, and 5 be filter plate.
Specific embodiment
The present invention is described further with reference to embodiments, it should be noted that the embodiment cannot function as pair
The limitation of the scope of the present invention, any improvement made on the basis of the present invention is all without prejudice to spirit of that invention.Institute of the present invention
It can be commercially commercially available unless otherwise specified with raw material or equipment.
Embodiment 1
Prepare compound:
By reaction equation: 2SnCl2+3B2O3→Sn2B5O9Cl+BCl3, compound Sn is synthesized using solid reaction process2B5O9Cl:
By SnCl2, B2O32:3 is uniformly mixed in molar ratio, is packed into platinum crucible, is placed in Muffle furnace, in vacuum or inertia
Under atmosphere, it is warming up to 450 DEG C, constant temperature 48 hours is to get arriving compound Sn2B5O9The polycrystal powder of Cl.
Embodiment 2
Prepare compound:
By reaction equation: 2SnCl2+5H3BO3→Sn2B5O9Cl+6H2O+3HCl synthesizes compound using solid reaction process
Sn2B5O9Cl:
By SnCl2, H3BO32:5 is uniformly mixed in molar ratio, is packed into platinum crucible, is placed in Muffle furnace in vacuum or inertia
Under atmosphere, it is warming up to 450 DEG C, constant temperature 24 hours is to get arriving compound Sn2B5O9The polycrystal powder of Cl.
Embodiment 3
Prepare compound:
By reaction equation: SnO+SnCl2+2B2O3+H3BO3→Sn2B5O9Cl+HCl+H2O synthesizes chemical combination using solid reaction process
Object Sn2B5O9Cl:
By SnO, SnCl2, B2O3, H3BO3It is uniformly mixed in the ratio of the reaction equation in embodiment 3, is packed into platinum crucible, sets
In Muffle furnace, in a vacuum or inert atmosphere, it is warming up to 450 DEG C, constant temperature 120 hours is to get arriving compound Sn2B5O9Cl's
Polycrystal powder.
Embodiment 4
Prepare compound:
By reaction equation: SnO+2SnCl2+5SnB4O7→4Sn2B5O9Cl synthesizes compound using solid reaction process
SnB4O6Cl:
By SnO, SnCl2, SnB4O71:2:5 is uniformly mixed in molar ratio, is packed into platinum crucible, is placed in Muffle furnace true
Under empty or inert atmosphere, it is warming up to 450 DEG C, constant temperature 72 hours is to get arriving compound Sn2B5O9The polycrystal powder of Cl.
Embodiment 5
Prepare compound:
By reaction equation: 2SnCl2+3B2O3→Sn2B5O9Cl+BCl3, compound Sn is synthesized using Vacuum Package method2B5O9Cl:
By SnCl2, B2O32:3 is uniformly mixed in molar ratio, is fitted into the quartz ampoule of Φ 40mm, quartz ampoule is vacuumized, very
Reciprocal of duty cycle reaches 1 × 10-3Pa, elevated-temperature seal are placed in Muffle furnace, are warming up to 450 DEG C with the rate of 10 DEG C/h of temperature, constant temperature 24
Hour to get arrive compound Sn2B5O9The polycrystal powder of Cl.
Embodiment 6
Prepare compound:
By reaction equation: 2SnCl2+5H3BO3→Sn2B5O9Cl+6H2O+3HCl synthesizes compound using Vacuum Package method
Sn2B5O9Cl:
By SnCl2, H3BO32:5 is uniformly mixed in molar ratio, is fitted into the quartz ampoule of Φ 40mm, quartz ampoule is vacuumized,
Vacuum degree reaches 1 × 10-3Pa, elevated-temperature seal are placed in Muffle furnace, are warming up to 450 DEG C with the rate of 5 DEG C/h of temperature, constant temperature 72
Hour to get arrive compound Sn2B5O9The polycrystal powder of Cl.
Embodiment 7
Prepare compound:
By reaction equation: SnO+SnCl2+2B2O3+H3BO3→Sn2B5O9Cl+HCl+H2O synthesizes chemical combination using Vacuum Package method
Object Sn2B5O9Cl:
By SnO, SnCl2, B2O3, H3BO3It is uniformly mixed in the ratio of the reaction equation in embodiment 7, is packed into the stone of Φ 40mm
Ying Guanzhong vacuumizes quartz ampoule, and vacuum degree reaches 1 × 10-3Pa, elevated-temperature seal are placed in Muffle furnace, with 8 DEG C/h's of temperature
Rate is warming up to 450 DEG C, and constant temperature 72 hours is to get arriving compound Sn2B5O9The polycrystal powder of Cl.
Embodiment 8
Prepare compound:
By reaction equation: SnO+2SnCl2+5SnB4O7→4Sn2B5O9Cl synthesizes compound using Vacuum Package method
Sn2B5O9Cl:
By SnO, SnCl2, SnB4O71:2:5 is uniformly mixed in molar ratio, is fitted into the quartz ampoule of Φ 40mm, by quartz ampoule
It vacuumizes, vacuum degree reaches 1 × 10-3Pa, elevated-temperature seal are placed in Muffle furnace, are warming up to 450 with the rate of 5 DEG C/h of temperature
DEG C, constant temperature 96 hours is to get arriving compound Sn2B5O9The polycrystal powder of Cl.
Embodiment 9
Melt method for growing Sn2B5O9Cl nonlinear optical crystal:
Any compound Sn being prepared according to embodiment 1-82B5O9Cl polycrystal powder is packed into platinum crucible, is placed in horse
Not in furnace, in a vacuum or inert atmosphere, 750 DEG C is warming up to, constant temperature 80 hours, obtains blend melt；
Obtained blend melt is slowly dropped to 300 DEG C with the rate temperature of 0.1 DEG C/h of temperature, then with 5 DEG C/h's of temperature
Rate fast cooling obtains Sn to room temperature2B5O9Cl seed crystal；
Using Czochralski grown crystal: obtained seed crystal being fixed on seed rod, from equipped with blend melt obtained
Seed crystal under top, is turned by the crystalline substance that crystal growth controller applies 2rpm, seed crystal is lifted with 1mm/ days speed, with temperature 0.1
DEG C/cooling of the rate of h, to get to having a size of 18mm × 15mm × 10mm Sn after crystal growth stopping2B5O9Cl is non-linear
Optical crystal.
Embodiment 10
Melt method for growing Sn2B5O9Cl nonlinear optical crystal:
Any compound Sn being prepared according to embodiment 1-82B5O9Cl polycrystal powder is packed into platinum crucible, is placed in horse
Not in furnace, in a vacuum or inert atmosphere, 600 DEG C is warming up to, constant temperature 10 hours, obtains blend melt；
Obtained blend melt is slowly dropped to 300 DEG C with the rate temperature of 1 DEG C/h of temperature, then with the speed of 8 DEG C/h of temperature
Rate fast cooling obtains Sn to room temperature2B5O9Cl seed crystal；
Using Czochralski grown crystal: obtained seed crystal being fixed on seed rod, from equipped with blend melt obtained
Seed crystal under top, is turned by the crystalline substance that crystal growth controller applies 10rpm, seed crystal is lifted with 5mm/ days speed, with temperature 5
DEG C/cooling of the rate of h, to get to having a size of 10mm × 12mm × 8mm Sn after crystal growth stopping2B5O9Cl nonlinear optical
Learn crystal.
Embodiment 11
Melt method for growing Sn2B5O9Cl nonlinear optical crystal:
Any compound Sn being prepared according to embodiment 1-82B5O9Cl polycrystal powder is packed into platinum crucible, is placed in horse
Not in furnace, in a vacuum or inert atmosphere, 800 DEG C is warming up to, constant temperature 120 hours, obtains blend melt；
Obtained blend melt is slowly dropped to 300 DEG C with the rate temperature of 2 DEG C/h of temperature, then with the speed of 10 DEG C/h of temperature
Rate fast cooling obtains Sn to room temperature2B5O9Cl seed crystal；
Using Czochralski grown crystal: obtained seed crystal being fixed on seed rod, from equipped with blend melt obtained
Seed crystal under top, is turned by the crystalline substance that crystal growth controller applies 20rpm, seed crystal is lifted with 10mm/ days speed, with temperature 10
DEG C/cooling of the rate of h, to get to having a size of 10mm × 10mm × 5mm Sn after crystal growth stopping2B5O9Cl nonlinear optical
Learn crystal.
Embodiment 12
Melt method for growing Sn2B5O9Cl nonlinear optical crystal:
Any compound Sn being prepared according to embodiment 1-82B5O8Cl polycrystal powder is packed into platinum crucible, is placed in horse
Not in furnace in a vacuum or inert atmosphere, 600 DEG C are warming up to, constant temperature 50 hours, obtains blend melt；
Obtained blend melt is slowly dropped to 300 DEG C with the rate of 1 DEG C/h, then extremely with the rate fast cooling of 8 DEG C/h
Room temperature obtains Sn2B5O9Cl seed crystal；
Crystal is grown using kyropoulos: obtained seed crystal is fixed on seed rod, from equipped with blend melt obtained
Seed crystal under top is cooled down with the rate of 0.1 DEG C/h of temperature, makes crystal growth 5 hours, is slowly promoted crystal but is not departed from liquid level,
Continued growth so repeats, to get to having a size of 15mm × 15mm × 12mm Sn after crystal growth stopping2B5O9Cl is non-thread
Property optical crystal.
Embodiment 13
Melt method for growing Sn2B5O9Cl nonlinear optical crystal:
Any compound Sn being prepared according to embodiment 1-82B5O8Cl polycrystal powder is packed into platinum crucible, is placed in horse
Not in furnace in a vacuum or inert atmosphere, 700 DEG C are warming up to, constant temperature 120 hours, obtains blend melt；
Obtained blend melt is slowly dropped to 300 DEG C with the rate of 0.1 DEG C/h, then with the rate fast cooling of 5 DEG C/h
To room temperature, Sn is obtained2B5O9Cl seed crystal；
Crystal is grown using kyropoulos: obtained seed crystal is fixed on seed rod, from equipped with blend melt obtained
Seed crystal under top is cooled down with the rate of 10 DEG C/h of temperature, makes crystal growth 15 hours, is slowly promoted crystal but is not departed from liquid level,
Continued growth so repeats, to get to having a size of 10mm × 12mm × 10mm Sn after crystal growth stopping2B5O9Cl is non-thread
Property optical crystal.
Embodiment 14
Melt method for growing Sn2B5O9Cl nonlinear optical crystal:
Any compound Sn being prepared according to embodiment 1-82B5O8Cl polycrystal powder is packed into platinum crucible, is placed in horse
Not in furnace in a vacuum or inert atmosphere, 800 DEG C are warming up to, constant temperature 10 hours, obtains blend melt；
Obtained blend melt is slowly dropped to 300 DEG C with the rate of 2 DEG C/h, then extremely with the rate fast cooling of 10 DEG C/h
Room temperature obtains Sn2B5O9Cl seed crystal；
Crystal is grown using kyropoulos: obtained seed crystal is fixed on seed rod, from equipped with blend melt obtained
Seed crystal under top is cooled down with the rate of 5 DEG C/h of temperature, makes crystal growth 10 hours, is slowly promoted crystal but is not departed from liquid level, after
Continuous growth, so repeats, to get to having a size of 12mm × 12mm × 10mm Sn after crystal growth stopping2B5O9Cl is non-linear
Optical crystal.
Embodiment 15
Melt method for growing Sn2B5O9Cl nonlinear optical crystal:
Any compound Sn being prepared according to embodiment 1-82B5O8Cl polycrystal powder is packed into platinum crucible, is placed in horse
Not in furnace in a vacuum or inert atmosphere, 800 DEG C are warming up to, constant temperature 100 hours, obtains blend melt；
Obtained blend melt is slowly dropped to 300 DEG C with the rate of 2 DEG C/h, then extremely with the rate fast cooling of 10 DEG C/h
Room temperature obtains Sn2B5O9Cl seed crystal；
Crystal is grown in compound melt using Bridgman-Stockbarger method: obtained seed crystal being placed on crucible bottom, then will be real
Apply the compound Sn of the preparation of example 52B5O9Cl polycrystal powder is put into crucible, then seals platinum crucible, will grow furnace temperature liter
To 750 DEG C, constant temperature 10 hours, adjustment bushing position keeps seed crystal micro- molten, then crucible is reduced with 1mm/ days speed, with temperature 3
DEG C/rate of temperature fall of h is down to 350 DEG C, after to be grown, then is down to room temperature quickly with the rate of 10 DEG C/h of temperature to get arriving
Having a size of 16mm × 15mm × 13mm Sn2B5O9Cl nonlinear optical crystal.
Embodiment 16
Melt method for growing Sn2B5O9Cl nonlinear optical crystal:
Any compound Sn being prepared according to embodiment 1-82B5O8Cl polycrystal powder is packed into platinum crucible, is placed in horse
Not in furnace in a vacuum or inert atmosphere, 600 DEG C are warming up to, constant temperature 10 hours, obtains blend melt；
Obtained blend melt is slowly dropped to 300 DEG C with the rate of 0.1 DEG C/h, then with the rate fast cooling of 5 DEG C/h
To room temperature, Sn is obtained2B5O9Cl seed crystal；
Crystal is grown in compound melt using Bridgman-Stockbarger method: obtained seed crystal being placed on crucible bottom, then will be real
Apply the compound Sn of the preparation of example 52B5O9Cl polycrystal powder is put into crucible, then seals platinum crucible, will grow furnace temperature liter
To 550 DEG C, constant temperature 80 hours, adjustment bushing position keeps seed crystal micro- molten, then reduces crucible with 5mm/ days speed, meanwhile, it protects
It is constant to hold growth temperature, after to be grown, then room temperature is down to quickly to get to having a size of 20mm with the rate of 5 DEG C/h of temperature
The Sn of × 15mm × 12mm2B5O9Cl nonlinear optical crystal.
Embodiment 17
Melt method for growing Sn2B5O9Cl nonlinear optical crystal:
Any compound Sn being prepared according to embodiment 1-82B5O8Cl polycrystal powder is packed into platinum crucible, is placed in horse
Not in furnace in a vacuum or inert atmosphere, 700 DEG C are warming up to, constant temperature 120 hours, obtains blend melt；
Obtained blend melt is slowly dropped to 300 DEG C with the rate of 1 DEG C/h, then extremely with the rate fast cooling of 8 DEG C/h
Room temperature obtains Sn2B5O9Cl seed crystal；
Crystal is grown in compound melt using Bridgman-Stockbarger method: obtained seed crystal being placed on crucible bottom, then will be real
Apply the compound Sn of the preparation of example 52B5O9Cl polycrystal powder is put into crucible, then seals platinum crucible, will grow furnace temperature liter
To 650 DEG C, constant temperature 120 hours, adjustment bushing position keeps seed crystal micro- molten, then crucible is reduced with 1mm/ days speed, with temperature 3
DEG C/rate of temperature fall of h is down to 350 DEG C, after to be grown, then room temperature is down to quickly to get to ruler with the rate of 8 DEG C/h of temperature
Very little is 16mm × 14mm × 12mm Sn2B5O9Cl nonlinear optical crystal.
Embodiment 18
High temperature solution method grows Sn2B5O9Cl nonlinear optical crystal:
Any compound Sn being prepared according to embodiment 1-82B5O9Cl polycrystal powder and cosolvent B2O3In molar ratio 1
: 0.1 is uniformly mixed, and is fitted into platinum crucible, is warming up to 750 DEG C, constant temperature 5 hours, obtains mixed molten liquid；Platinum crucible is packed into,
It is placed in Muffle furnace, in a vacuum or inert atmosphere, is warming up to 750 DEG C, constant temperature 10 hours, obtains blend melt；
It prepares seed crystal: obtained mixed molten liquid is placed in single crystal growing furnace, be slowly dropped to 350 with the rate of 0.1 DEG C/h of temperature
DEG C, then Sn is obtained to room temperature with the rate fast cooling of 5 DEG C/h of temperature2B5O9Cl seed crystal；
Growth crystal: obtained seed crystal is fixed on seed rod, from equipped with mixed molten liquid obtained top under seed crystal,
Turned by the crystalline substance that crystal growth controller applies 2rpm, cooled down with the rate of 0.1 DEG C/h of temperature, after crystal growth stopping, i.e.,
It obtains having a size of 28mm × 25mm × 13mm Sn2B5O9Cl nonlinear optical crystal.
Embodiment 19
High temperature solution method grows Sn2B5O9Cl nonlinear optical crystal:
Any compound Sn being prepared according to embodiment 1-82B5O9Cl polycrystal powder and cosolvent SnCl2By mole
It is uniformly mixed than 1: 1, is fitted into platinum crucible, in a vacuum or inert atmosphere, is warming up to 550 DEG C, constant temperature 120 hours, obtains
Mixed molten liquid；
It prepares seed crystal: obtained mixed molten liquid is placed in single crystal growing furnace, be slowly dropped to 350 DEG C with the rate of 2 DEG C/h of temperature,
Sn is obtained to room temperature with the rate fast cooling of 10 DEG C/h of temperature again2B5O9Cl seed crystal；
Growth crystal: obtained seed crystal is fixed on seed rod, from equipped with mixed molten liquid obtained top under seed crystal,
Turned by the crystalline substance that crystal growth controller applies 20rpm, cooled down with the rate of 3 DEG C/h of temperature, after crystal growth stopping to get
To having a size of 25mm × 22mm × 12mm Sn2B5O9Cl nonlinear optical crystal.
Embodiment 20
High temperature solution method grows Sn2B5O9Cl nonlinear optical crystal:
Any compound Sn being prepared according to embodiment 1-82B5O9Cl polycrystal powder and cosolvent H3BO3In molar ratio
Be uniformly mixed at 1: 6, is fitted into platinum crucible, in a vacuum or inert atmosphere, is warming up to 730 DEG C, constant temperature 52 hours, is mixed
Melt；
It prepares seed crystal: obtained mixed molten liquid is placed in single crystal growing furnace, be slowly dropped to 350 DEG C with the rate of 1 DEG C/h of temperature,
Sn is obtained to room temperature with the rate fast cooling of 8 DEG C/h again2B5O9Cl seed crystal；
Growth crystal: obtained seed crystal is fixed on seed rod, from equipped with mixed molten liquid obtained top under seed crystal,
Turned by the crystalline substance that crystal growth controller applies 10rpm, cooled down with the rate of 1 DEG C/h of temperature, after crystal growth stopping to get
To having a size of 14mm × 12mm × 10mm SnB4O6CL nonlinear optical crystal.
Embodiment 21
Vacuum Package method grows Sn2B5O9Cl nonlinear optical crystal:
Any compound Sn being prepared according to embodiment 1-82B5O9The quartz ampoule of Cl polycrystal powder loading Φ 40mm
In, quartz ampoule is vacuumized, vacuum degree reaches 1 × 10-3Pa, elevated-temperature seal are placed in Muffle furnace, are warming up to 650 DEG C, constant temperature 5
Hour, 350 DEG C then are cooled to the rate of 0.1 DEG C/h of temperature, then with the rate fast cooling of 8 DEG C/h of temperature to room temperature, i.e.,
It obtains having a size of 4mm × 4mm × 2mm Sn2B5O9Cl nonlinear optical crystal.
Embodiment 22
Vacuum Package method grows Sn2B5O9Cl nonlinear optical crystal:
Any compound Sn being prepared according to embodiment 1-82B5O9Cl polycrystal powder and cosolvent SnCl2By mole
It is uniformly mixed than 1: 1, is fitted into the quartz ampoule of Φ 40mm, quartz ampoule is vacuumized, vacuum degree reaches 1 × 10-3Pa, elevated-temperature seal
It is placed in Muffle furnace, is warming up to 600 DEG C, constant temperature 100 hours, be then cooled to 350 DEG C with the rate of 0.1 DEG C/h of temperature, then
With the rate fast cooling of 5 DEG C/h of temperature to room temperature to get to having a size of 5mm × 5mm × 3mm Sn2B5O9Cl crystal.
Embodiment 23
Vacuum Package method grows Sn2B5O9Cl nonlinear optical crystal:
Any compound Sn being prepared according to embodiment 1-82B5O9Cl polycrystal powder and cosolvent H3BO3In molar ratio
Be uniformly mixed at 1: 6, is fitted into the quartz ampoule of Φ 40mm, quartz ampoule is vacuumized, vacuum degree reaches 1 × 10-3Pa, after elevated-temperature seal
It is placed in Muffle furnace, is warming up to 550 DEG C, constant temperature 50 hours, is then cooled to 350 DEG C with the rate of 2 DEG C/h of temperature, then with temperature
The rate fast cooling of 10 DEG C/h is to room temperature to get to having a size of 3mm × 3mm × 2mm Sn2B5O9Cl nonlinear optical crystal.
Embodiment 24
Vacuum Package method grows Sn2B5O9Cl nonlinear optical crystal:
Any compound Sn being prepared according to embodiment 1-82B5O9Cl polycrystal powder and cosolvent B2O3In molar ratio 1
: 0.1 is uniformly mixed, and is fitted into the quartz ampoule of Φ 40mm, quartz ampoule is vacuumized, vacuum degree reaches 1 × 10-3Pa, elevated-temperature seal
It is placed in Muffle furnace, is warming up to 705 DEG C, constant temperature 120 hours, be then cooled to 350 DEG C with the rate of 1 DEG C/h of temperature, then with
The rate fast cooling of 8 DEG C/h of temperature is to room temperature to get to having a size of 4mm × 3mm × 2mm Sn2B5O9Cl non-linear optical crystal
Body.
Embodiment 25
Hydrothermal Growth tin boron oxygen chlorine nonlinear optical crystal:
Any compound Sn being prepared according to embodiment 1-82B5O9It is dissolved in Cl polycrystal powder merging deionized water,
By the mixture of endless fully dissolved in temperature 60 C ultrasonication, dissolution is mixed them thoroughly；With HCl and NH3·H2O is adjusted
PH value is 9；
Obtained mixed solution is transferred in the liner for the autoclave that clean, free of contamination volume is 100mL, and
By reaction kettle screwing hermetic；
Autoclave is placed in insulating box, is warming up to 150 DEG C, constant temperature 8 days, then with the cooling speed of 5 DEG C/day of temperature
Rate is down to room temperature；It obtains having a size of 5mm × 3mm × 2mm Sn2B5O9Cl nonlinear optical crystal.
Embodiment 26
Solution at room temperature method grows tin boron oxygen chlorine nonlinear optical crystal:
Any compound Sn being prepared according to embodiment 1-82B5O9Cl polycrystal powder is put into the glass container of wash clean
In, 20mL deionized water is added, then ultrasonication makes to be sufficiently mixed dissolution, with HCl and NH3·H2O adjusts solution ph
9, mixed solution is obtained by filtration with filter paper；
Obtained mixed solution is placed in clean triangular flask, is sealed with pan paper, is placed on without shaking, pollution-free, nothing
In cross-ventilated static environment, evaporation rate of several apertures to adjust water in aqueous solution is pricked into sealing, at room temperature
Stand 5 days；
Crystal grain is grown in container bottom to solution, until the no longer significant change of crystal grain size, obtains seed crystal；
The preferable seed crystal of quality is selected, is hung in mixed solution obtained, stands growth at room temperature 30 days i.e.
It can be obtained having a size of 10mm × 8mm × 6mm Sn2B5O9Cl nonlinear optical crystal.
Embodiment 27
By the resulting any Sn of embodiment 9-262B5O9Cl crystal is placed in 3 by shown in attached drawing 3 by the direction processing that matches
Position on, at room temperature, with adjust Q-Nd:YAG laser light source, incident wavelength 1064nm, by adjust Q Nd:YAG laser
Device 1 issues the infrared beam 2 that wavelength is 1064nm and injects Sn2B5O9Cl monocrystalline 3, generation wavelength are the green frequency doubled light of 532nm,
Output intensity is about 0.5 times of equal conditions KDP.
Claims (7)
1. a kind of compound tin boron oxygen chlorine, it is characterised in that the chemical formula of the compound is Sn2B5O9Cl, molecular weight 470.70,
It is made of solid-phase synthesis or Vacuum Package method.
2. a kind of preparation method of compound tin boron oxygen chlorine as described in claim 1, it is characterised in that use solid-phase synthesis
Or the preparation of Vacuum Package method, concrete operations follow these steps to carry out:
The solid-phase synthesis prepare compound tin boron oxygen chlorine:
Sn compound, boride alloy and compound containing Cl will be contained to be uniformly mixed at Sn: B: Cl=2: 5: 1 in molar ratio, be packed into platinum
Crucible is placed in Muffle furnace in a vacuum or inert atmosphere, is warming up to 400-700 DEG C, and constant temperature 24-120 hours is to get arriving chemical combination
Object Sn2B5O9Cl, the SnO of compound containing Sn, SnCl2Or SnB4O7；Boride alloy H3BO3、B2O3Or SnB4O7；It is to change containing Cl
Close object SnCl2；
The Vacuum Package method prepare compound tin boron oxygen chlorine:
Sn compound, boride alloy and compound containing Cl will be contained to be uniformly mixed at Sn: B: Cl=2: 5: 1 in molar ratio, be packed into quartz
Guan Zhong vacuumizes quartz ampoule, and vacuum degree reaches 1 × 10−3Pa, elevated-temperature seal are placed in Muffle furnace, with the speed of 5-10 DEG C/h
Rate is warming up to 400-700 DEG C, and constant temperature 24-120 hours is to get arriving compound Sn2B5O9Cl, wherein the compound containing Sn is
SnO、SnCl2Or SnB4O7；Boride alloy is H3BO3、B2O3Or SnB4O7；It is compound SnCl containing Cl2。
3. a kind of tin boron oxygen chlorine nonlinear optical crystal, it is characterised in that the chemical formula of the crystal is Sn2B5O8Cl, molecular weight are
470.70, belong to rhombic system, space group isPnn2, cell parameter isa =11.281 (3),b =11.331 (3),c =
6.5573 (19),α=90 °,β=90 °,γ=90 °, unit-cell volume is 838.2 (4)3。
4. a kind of preparation method of tin boron oxygen chlorine nonlinear optical crystal as claimed in claim 3, it is characterised in that using molten
Body method, high temperature solution method, Vacuum Package method, hydro-thermal method or solution at room temperature method grow crystal；
The concrete operations of the melt method for growing tin boron oxygen chlorine nonlinear optical crystal follow these steps to carry out:
A, Sn compound, boride alloy and compound containing Cl will be contained to be uniformly mixed at Sn: B: Cl=2: 5: 1 in molar ratio, be packed into platinum
Golden crucible is placed in Muffle furnace in a vacuum or inert atmosphere, is warming up to 400-600 DEG C, and constant temperature 24-120 hours is to get arriving
Sn2B5O9Cl polycrystal powder, wherein the compound containing Sn is SnO, SnCl2Or SnB4O7；Boride alloy is H3BO3、B2O3Or
SnB4O7；It is compound SnCl containing Cl2；
B, the Sn for obtaining step a2B5O8Cl polycrystal powder is packed into platinum crucible, is placed in Muffle furnace in vacuum or inert atmosphere
Under, it is warming up to 600-800 DEG C, constant temperature 10-120 hours, obtains blend melt；
C, the blend melt that step b is obtained is slowly dropped to 300 DEG C with the rate of 0.1-2 DEG C/h, then with the rate of 5-10 DEG C/h
Fast cooling obtains Sn to room temperature2B5O9Cl seed crystal；
D, crystal is grown in blend melt using czochralski method: the obtained seed crystal of step c is fixed on seed rod, from step b
Seed crystal under the top of blend melt obtained is turned by the crystalline substance that crystal growth controller applies 2-20rpm, with 1-10 mm/'s days
Speed lifts seed crystal, while with the cooling of the rate of 0.1-10 DEG C/h, arriving Sn after crystal growth stopping2B5O8Cl is non-linear
Optical crystal；
Or crystal is grown in blend melt with kyropoulos: the obtained seed crystal of step c is fixed on seed rod, from step b system
Seed crystal under the top of the blend melt obtained is cooled down with the rate of 0.1-10 DEG C/h of temperature, makes crystal growth 5-15 hours, slowly mention
It rises crystal but does not depart from liquid level continued growth, so repeat, arrive Sn after crystal growth stopping2B5O9Cl nonlinear optics
Crystal；
Or crystal is grown in blend melt with Bridgman-Stockbarger method: the obtained seed crystal of step c is placed on crucible bottom, then by step
The Sn of a preparation2B5O9Cl polycrystalline is put into crucible, then seals platinum crucible, growth furnace temperature is risen to 550-750 DEG C, perseverance
10-120 hours warm, adjustment bushing position keeps seed crystal micro- molten, then reduces crucible with the speed of 1-10 mm/ days, meanwhile, it keeps
Growth temperature is constant, or is down to 350 DEG C, after to be grown with prestissimo with the rate of temperature fall of 3 DEG C/h, then with 5-10 DEG C/
The rate of h is down to room temperature quickly to get Sn is arrived2B5O9Cl nonlinear optical crystal；
The concrete operations of the high temperature solution method growth tin boron oxygen chlorine nonlinear optical crystal follow these steps to carry out:
A, Sn compound, boride alloy and compound containing Cl will be contained to be uniformly mixed at Sn: B: Cl=2: 5: 1 in molar ratio, be packed into platinum
Golden crucible is placed in Muffle furnace in a vacuum or inert atmosphere, is warming up to 400-600 DEG C, and constant temperature 24-120 hours is to get arriving
Sn2B5O9Cl polycrystal powder, wherein the compound containing Sn is SnO, SnCl2Or SnB4O7；Boride alloy is H3BO3、B2O3Or
SnB4O7；It is compound SnCl containing Cl2；
B, the Sn for obtaining step a2B5O9Cl polycrystal powder 1: 0.1-6 is uniformly mixed in molar ratio with cosolvent, is reloaded into platinum
In crucible, it is warming up to 500-800 DEG C, constant temperature 5-120 hours, obtains mixed molten liquid；Wherein the cosolvent is SnCl2、H3BO3
Or B2O3；
C, it prepares seed crystal: the obtained mixed molten liquid of step b is placed in single crystal growing furnace, be slowly dropped to 350 with the rate of 0.1-2 DEG C/h
DEG C, then Sn is obtained to room temperature with the rate fast cooling of 5-10 DEG C/h2B5O9Cl seed crystal；
D, it grows crystal: the obtained seed crystal of step c is fixed on seed rod, under the top of the mixed molten liquid made from the step b
Seed crystal is turned by the crystalline substance that crystal growth controller applies 2-20rpm, is cooled down with the rate of 0.1-3 DEG C/h, stopped to crystal growth
Afterwards to get arrive Sn2B5O9Cl nonlinear optical crystal；
The concrete operations of the Vacuum Package method growth tin boron oxygen chlorine nonlinear optical crystal follow these steps to carry out:
A, Sn compound, boride alloy and compound containing Cl will be contained to be uniformly mixed at Sn: B: Cl=2: 5: 1 in molar ratio, be packed into platinum
Golden crucible is placed in Muffle furnace in a vacuum or inert atmosphere, is warming up to 400-600 DEG C, and constant temperature 24-120 hours is to get arriving
Sn2B5O9Cl polycrystal powder, wherein the compound containing Sn is SnO, SnCl2Or SnB4O7；Boride alloy is H3BO3、B2O3Or
SnB4O7；It is compound SnCl containing Cl2；
B, the Sn for obtaining step a2B5O9Cl polycrystal powder 0-1: 0.1-6 is uniformly mixed in molar ratio with cosolvent, is packed into quartz
Guan Zhong, elevated-temperature seal are placed in Muffle furnace, are warming up to 500-800 DEG C, and constant temperature 5-120 hours, then with the speed of 0.1-3 DEG C/h
Rate is cooled to 350 DEG C, then with the rate fast cooling of 5-10 DEG C/h to room temperature to get arriving Sn2B5O9Cl nonlinear optical crystal,
Wherein the cosolvent is SnCl2、H3BO3Or B2O3；
The concrete operations of the Hydrothermal Growth tin boron oxygen chlorine nonlinear optical crystal follow these steps to carry out:
A, Sn compound, boride alloy and compound containing Cl will be contained to be uniformly mixed at Sn: B: Cl=2: 5: 1 in molar ratio, be packed into platinum
Golden crucible, is placed in Muffle furnace, in a vacuum or inert atmosphere, is warming up to 400-600 DEG C, and constant temperature 24-120 hours is to get arriving
Sn2B5O9Cl polycrystal powder, wherein the compound containing Sn is SnO, SnCl2Or SnB4O7；Boride alloy is H3BO3、B2O3Or
SnB4O7；Compound containing Cl is SnCl2；
B, the SnB for obtaining step a4O6It is dissolved in Cl polycrystal powder merging deionized water, by the mixture of endless fully dissolved in temperature
60 DEG C of ultrasonications are spent, dissolution is mixed them thoroughly, with HCl and NH3·H2It is 8-11 that O, which adjusts pH value, obtains mixed solution；
C, the obtained mixed solution of step b is transferred to the liner for the autoclave that clean, free of contamination volume is 100 mL
In, and by reaction kettle screwing hermetic；
D, autoclave is placed in insulating box, is warming up to 150-350 DEG C, constant temperature 5-8 days, then with 5-20 DEG C/day of drop
Warm rate is down to room temperature to get Sn is arrived2B5O9Cl nonlinear optical crystal；
The concrete operations of the solution at room temperature method growth tin boron oxygen chlorine nonlinear optical crystal follow these steps to carry out:
A, Sn compound, boride alloy and compound containing Cl will be contained to be uniformly mixed at Sn: B: Cl=2: 5: 1 in molar ratio, be packed into platinum
Golden crucible is placed in Muffle furnace in a vacuum or inert atmosphere, is warming up to 400-600 DEG C, and constant temperature 24-120 hours is to get arriving
Sn2B5O9Cl polycrystal powder, wherein the compound containing Sn is SnO, SnCl2Or SnB4O7；Boride alloy is H3BO3、B2O3Or
SnB4O7；It is compound SnCl containing Cl2；
B, the Sn for obtaining step a2B5O9Cl polycrystal powder is put into the glass container of wash clean, and 20-100mL deionization is added
Water, then ultrasonication makes to be sufficiently mixed dissolution, with HCl and NH3·H2It is 8-11 that O, which adjusts pH value, is obtained by filtration with filter paper mixed
Close solution；
C, the obtained mixed solution of step b is placed in clean glass container, is sealed with pan paper, is placed on without shaking, without dirt
It contaminates, without in cross-ventilated static environment, evaporation rate of several apertures to adjust water in aqueous solution is pricked into sealing, in room
Temperature is lower to stand 5-20 days；
D, crystal grain is grown in container bottom to the solution in step c, until the no longer significant change of crystal grain size, obtains
Seed crystal；
E, the preferable seed crystal of quality in step d is selected, is hung in mixed solution made from step b, is stood at room temperature
10-30 days are grown to get Sn is arrived2B5O9Cl nonlinear optical crystal.
5. a kind of tin boron oxygen chlorine nonlinear optical crystal as claimed in claim 3 is preparing what Nd:YAG laser was exported
The fundamental frequency light of 1064nm carries out 2 frequencys multiplication, the purposes of 3 multiplied frequency harmonic light outputs.
6. short wavelength's frequency multiplication that a kind of tin boron oxygen chlorine nonlinear optical crystal as claimed in claim 5 generates 355nm in preparation
Purposes in light output.
7. a kind of tin boron oxygen chlorine nonlinear optical crystal as claimed in claim 3 is in preparation times frequency generator, up or down frequency
Purposes in converter or optical parametric oscillator.
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| CN110618476A (en) * | 2019-09-27 | 2019-12-27 | 中国科学院新疆理化技术研究所 | Application of tin boron oxygen chlorine birefringent crystal |
| CN111593406A (en) * | 2020-06-02 | 2020-08-28 | 中国科学院新疆理化技术研究所 | Compound tin boron oxygen bromine and tin boron oxygen bromine birefringent crystal, and preparation method and application thereof |
| CN111621848A (en) * | 2020-06-02 | 2020-09-04 | 中国科学院新疆理化技术研究所 | Compound tin boron oxygen bromine, tin boron oxygen bromine nonlinear optical crystal, preparation method and application |
| CN113913936A (en) * | 2021-10-28 | 2022-01-11 | 中国科学院新疆理化技术研究所 | Compound lanthanum boron oxygen fluorine and lanthanum boron oxygen fluorine nonlinear optical crystal, preparation method and application |
| CN114369870A (en) * | 2021-05-21 | 2022-04-19 | 四川九婴科技有限公司 | Ionothermal synthesis of nonlinear optical polycrystalline powder lead boron oxygen chloride |
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| CN110618476A (en) * | 2019-09-27 | 2019-12-27 | 中国科学院新疆理化技术研究所 | Application of tin boron oxygen chlorine birefringent crystal |
| CN111593406A (en) * | 2020-06-02 | 2020-08-28 | 中国科学院新疆理化技术研究所 | Compound tin boron oxygen bromine and tin boron oxygen bromine birefringent crystal, and preparation method and application thereof |
| CN111621848A (en) * | 2020-06-02 | 2020-09-04 | 中国科学院新疆理化技术研究所 | Compound tin boron oxygen bromine, tin boron oxygen bromine nonlinear optical crystal, preparation method and application |
| CN114369870A (en) * | 2021-05-21 | 2022-04-19 | 四川九婴科技有限公司 | Ionothermal synthesis of nonlinear optical polycrystalline powder lead boron oxygen chloride |
| CN113913936A (en) * | 2021-10-28 | 2022-01-11 | 中国科学院新疆理化技术研究所 | Compound lanthanum boron oxygen fluorine and lanthanum boron oxygen fluorine nonlinear optical crystal, preparation method and application |
| CN113913936B (en) * | 2021-10-28 | 2023-07-25 | 中国科学院新疆理化技术研究所 | Compound lanthanum boron oxyfluoride and lanthanum boron oxyfluoride nonlinear optical crystal, and preparation method and application thereof |
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