CN106757345A - The preparation method and purposes of sodium phosphate barium nonlinear optical crystal - Google Patents
The preparation method and purposes of sodium phosphate barium nonlinear optical crystal Download PDFInfo
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- CN106757345A CN106757345A CN201611025909.8A CN201611025909A CN106757345A CN 106757345 A CN106757345 A CN 106757345A CN 201611025909 A CN201611025909 A CN 201611025909A CN 106757345 A CN106757345 A CN 106757345A
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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
- C30B29/14—Phosphates
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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
- 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
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- G—PHYSICS
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- 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
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Abstract
The present invention relates to a kind of large scale sodium phosphate barium nonlinear optical crystal and preparation method and purposes, the crystal uses high temperature solution method, and crystal is grown with flux PbO, and nonlinear optical effect is about KDP (KH2PO4) 0.3 times；The crystal has mechanical strength moderate, easy processing, not the features such as deliquescence, speed is prepared simultaneously fast, simple to operate, low cost, the advantages of made crystalline size is big, it is adaptable to make nonlinear optics, laser system etc. is non-linear wait optics in can be widely used.
Description
Technical field
The present invention relates to a kind of preparation method and purposes of sodium phosphate barium nonlinear optical crystal, more particularly to using high temperature
Liquation method grows crystal.
Background technology
In modern laser technology, directly can be obtained optical maser wavelength using laser crystal very limited, from it is ultraviolet to
Infrared spectral region, remains in blank wave band.All solid state bluish-green laser system can produce near-infrared laser by solid state laser
Carry out frequency conversion by nonlinear optical crystal again to realize, in laser printing, optical storage of data, total colouring etc. is various
High-tech sector has important application prospect.
Deep ultraviolet nonlinear optical crystal is in industries such as semiconductor manufacturing industry, photoetching, laser system, the exploitations of precision instrument
Play significant role.The predominant non-linearity optical material for being applied to deep ultraviolet at present has：LiB3O5(LBO), Sr2Be2B2O7
(SBBO), CsBe2BO3F2(CBBF), and KBe2BO3F2(KBBF) etc., but above crystal is there are still respective deficiency
Place：As crystal growth is difficult, it is difficult to obtain large-size high-quality monocrystal, BeO has that severe toxicity, layer growth habit be serious, valency
Lattice costliness etc..Because the power output of superpower laser is inversely proportional with the cut-off side of nonlinear optical crystal, to improve Gao Gong
The power output of rate laser, it is necessary to find the shorter non-linear optical crystal material in cut-off side.Therefore, find and study new
The ultraviolet non-linear optical crystal material of moldeed depth is still when previous very important work.
Phosphate nonlinear optical crystal generally has short cut-off side, therefore is exploring deep ultraviolet nonlinear optical crystal
Field receives much concern.The non-linear phosphate crystal of deep ultraviolet having now been found that has：KBa2(PO3)5, Ba3P3O10X (X=Cl, Br),
RbBa2(PO3)5, Ba5P6O20, CsLa (PO3)4Deng, these crystal all have it is short by side and suitable frequency multiplication.
Claude Martin in 1972 et al. report BaNaP3O9Structure.By the investigation of document, so far there is not yet
To the BaNaP being enough to about preparation size for physical property measurement3O9The report of monocrystalline, in addition also not on BaNaP3O9Crystal
It is used to make the report of device for non-linear optical as the research of nonlinear optical material aspect of performance and its monocrystalline.
The content of the invention
Launch the blank spectral regions of optical maser wavelength the invention aims to make up all kinds of lasers, so as to provide one kind
With the sodium phosphate barium (BaNaP that Centimeter Level large scale is transparent3O9) nonlinear optical crystal；
It is a further object of the present invention to provide a kind of top-seeded solution growth of use flux, large scale BaNaP is prepared3O9It is non-linear
The method of optical crystal.
Another object of the present invention is to provide uses BaNaP3O9The purposes of the device for non-linear optical that monocrystalline makes.
Present invention aim at, there is provided a kind of preparation method and purposes of sodium phosphate barium nonlinear optical crystal, the method
It is fluxing agent growth crystal with PbO using high temperature solution method, the crystal molecule formula obtained by the method is BaNaP3O9, space
Group beP212121, cell parameter is：a =5.7765 (14),b =11.036 (3),c =12.257 (3),Z =
4,V = 781.4(3) Å3, nonlinear optical effect is about KDP (KH2PO4) 0.3 times；The crystal has mechanical strength moderate,
Easy processing, not the features such as deliquescence, while it is fast to prepare speed, simple to operate, low cost the advantages of made crystalline size is big, is applicable
In nonlinear optics is made, can be obtained in frequency-doubled conversion, the device for non-linear optical such as optical parametric oscillator extensively
Application.
A kind of preparation method of sodium phosphate barium nonlinear optical crystal of the present invention, concrete operations follow these steps into
OK：
A, sodium phosphate barium polycrystal powder obtained in high temperature solid-state method and flux PbO in molar ratio 1 will be used:0.1-5 is mixed
Close, be fitted into the opening platinum crucible of mm × 60 mm of Φ 60, be heated to 700-750 °C of temperature, constant temperature 1-100 h are obtained
The mixed molten liquid of sodium phosphate barium and flux；
B, will be tied with the corundum bar of platinum filament be put into step a preparation mixed molten liquid in, under immersed in liquid level, fast cooling to 630-
680 °C, then with the speed of 5-30 °C/d of temperature by mixed molten liquid slow cooling, the crystal on seed rod to be gathered in grows to one
When being sized, by crystal lift-off liquid level, room temperature is down to the speed of 5-50 °C/h of temperature, obtains small crystals as seed crystal；
C, mixed molten liquid is prepared again：It is in molar ratio 1 by sodium phosphate barium polycrystal powder and flux PbO:0.1-5 is mixed
Close, be fitted into the opening platinum crucible of mm × 60 mm of Φ 60, be heated to 700-750 °C, constant temperature 1-100 h, then lower the temperature
To 630-680 °C, the mixed molten liquid of sodium phosphate barium and flux is obtained, then the seed crystal platinum filament that step b is obtained is tied up in seed crystal
The lower end of bar, imports at crucible about 1-2 cm seed crystal from furnace roof portion aperture, and constant temperature 5-30 min are then immersed in mixed molten liquid
Below liquid level, fast cooling rotates seed crystal to 615-625 °C with the speed of 1-30 rpm, is slowly dropped with the speed of 1-5 °C/d
Temperature；
D, after crystal growth stopping after, by crystal lift-off liquid level, room temperature is down to the speed of 5-50 °C/h of temperature, then slowly
Crystal is taken out from burner hearth, you can obtain sodium phosphate barium nonlinear optical crystal.
The compound containing sodium is Na in step a sodium phosphate bariums2CO3、NaOH、NaNO3、Na2C2O4Or CH3COONa；Baric
Compound is BaCO3、Ba(OH)2、Ba(NO3)2、BaC2O4、(CH3COO)2Ba；Phosphorus-containing compound is NaH2PO4、Na3PO4、
BaHPO4、Ba3(PO4)2、NH4H2PO4。
Sodium phosphate barium and the amount ratio of the material of flux PbO are 1 in step a: 0.1-5.
Seed crystal in step c is fixed on seed rod for any direction.
By the sodium phosphate barium nonlinear optical crystal of the method acquisition as the purposes for preparing times frequency generator.
Sodium phosphate barium nonlinear optical crystal of the present invention can prepare the chemical combination using general chemical method
The polycrystal powder of thing, then the polycrystal powder and flux that will prepare mix, you can obtain the sodium phosphate barium with certain size non-
Linear optical crystal, the preferred high temperature solid-state method of polycrystal powder of preparation, i.e.,：The compound of sodium, the compound of baric will be contained and contained
The compound of phosphorus is mixed with stoichiometric proportion, and heating carries out solid phase reaction, you can obtain chemical formula for BaNaP3O9Compound.
Prepare BaNaP3O9The chemical equation of compound：
(1) Na2CO3 + 2BaCO3 + 6NH4H2PO4 → 2BaNaP3O9 + 3CO2↑+ 6NH3↑ + 6H2O↑
(2) Na2CO3 + 2Ba(NO3)2 + 6NH4H2PO4 →2BaNaP3O9 + CO2↑ + 4NO2↑ + 6NH3↑ + 6H2O↑
(3) 2NaOH + 2BaCO3 + 6NH4H2PO4 → 2BaNaP3O9 + 7H2O↑ + 2CO2↑ + 6NH3↑
(4) 2NaOH + 2Ba(NO3)2 + 6NH4H2PO4 → 2BaNaP3O9 + 7H2O↑ + 4NO2↑ + 6NH3↑
(5) NaNO3 + BaCO3 + 3NH4H2PO4 → BaNaP3O9 + NO2↑+ CO2↑ + 3NH3↑ + 3H2O↑
(6) NaNO3 + Ba(NO3)2 + 3NH4H2PO4 → BaNaP3O9 + 3NO2↑ + 3NH3↑ + 3H2O↑
(7) Na2C2O4 + 2BaCO3 + 6NH4H2PO4 → 2BaNaP3O9 + 4CO2↑ + 6NH3↑ + 6H2O↑
(8) 2CH3COONa + 2BaCO3 + 6NH4H2PO4 → 2BaNaP3O9 + 9H2O↑ + 6CO2↑ + 6NH3↑
Raw material uses commercially available reagent in the present invention, by method of the present invention, with simple to operate, fast growth,
The advantages of growth cycle is short.
Sodium phosphate barium nonlinear optical material prepared by the present invention is used as preparing device for non-linear optical.
The sodium phosphate barium nonlinear optical material is to optical manufacturing precision without particular/special requirement.
Brief description of the drawings
Fig. 1 is X-ray diffracting spectrum of the present invention；
Below in conjunction with accompanying drawing, the present invention is described in detail：
Embodiment 1：
By taking reaction equation (1) as an example, but it is not limited to reaction equation (1)：
Using high temperature solid-state method, with reaction equation Na2CO3 + 2BaCO3 + 6NH4H2PO4 → 2BaNaP3O9 + 3CO2↑ +
6NH3↑ + 6H2O↑
Synthesis sodium phosphate barium (BaNaP3O9) compound：By Na2CO3、BaCO3、NH4H2PO4Stoichiometrically 1: 2 :6 put
Enter in mortar, mix and carefully grind, be then charged into the opening corundum crucible of mm × 100 mm of Φ 100, compressed,
It is put into Muffle furnace, is to slowly warm up to 300 °C, the h of constant temperature 10 takes out crucible after cooling, takes out sample and re-grinds uniformly,
It is placed in crucible again, in 600 °C of h of constant temperature 48 of temperature in Muffle furnace, is drawn off, grinding obtains final product sodium phosphate in being put into mortar
Barium compound, carries out X-ray analysis to the product, gained X-ray spectrogram with it has been reported that result be consistent；
A, BaNaP obtained in high temperature solid-state method will be used3O9Polycrystal powder and flux PbO in molar ratio 1:0.3 is mixed,
It is fitted into the opening platinum crucible of mm × 50 mm of Φ 50, is heated to 750 °C of temperature, the h of constant temperature 50 obtains BaNaP3O9With help
The mixed molten liquid of flux；
B, will be tied with the corundum bar of platinum filament be put into step a preparation mixed molten liquid in, under immersed in liquid level, the min of constant temperature 30, quickly
650 °C are cooled to, then with the speed of 30 °C/d of temperature by mixed molten liquid slow cooling, the crystal on seed rod to be gathered in is long
During to required size, by crystal lift-off liquid level, room temperature is down to the speed of 40 °C/h, obtains small crystals as seed crystal；
C, mixed molten liquid is prepared again：By BaNaP3O9It is in molar ratio 1 that polycrystal powder mixes with flux PbO:0.3 is carried out
Mixing, is fitted into the opening platinum crucible of mm × 50 mm of Φ 50, is heated to 750 °C, the h of constant temperature 50, then is cooled to
650 °C, obtain BaNaP3O9With the mixed molten liquid of flux, then by step b obtain seed crystal platinum filament tie up under seed rod
End, from furnace roof portion aperture by seed crystal import at crucible about 1-2 cm, the min of constant temperature 20, be then immersed in mixed molten liquid liquid level with
Under, fast cooling rotates seed crystal, with the speed slow cooling of 5 °C/d to 625 °C with the speed of 30 rpm；
D, after crystal growth stopping after, by crystal lift-off liquid level, room temperature is down to the speed of 50 °C/h of temperature, then slowly from
Crystal is taken out in burner hearth, you can it is the BaNaP of 21 mm × 17 mm × 12 mm to obtain size3O9Nonlinear optical crystal.
Na in raw material2CO3Corresponding NaOH, NaNO can be used3、Na2C2O4Or CH3COONa is replaced, BaCO3Phase can be used
The Ba (OH) for answering2、Ba(NO3)2、BaC2O4、(CH3COO)2Ba is replaced, NH4H2PO4Corresponding NaH can be used2PO4、Na3PO4、
BaHPO4、Ba3(PO4)2Replace, can obtain sodium phosphate barium crystal.
Embodiment 2：
By taking reaction equation (2) as an example, but it is not limited to reaction equation (2)：
Using high temperature solid-state method, with reaction equation Na2CO3 + 2Ba(NO3)2 + 6NH4H2PO4 → 2BaNaP3O9 + CO2↑ +
4NO2↑ + 6NH3↑ + 6H2O↑
Synthesis sodium phosphate barium (BaNaP3O9) compound, concrete operation step carried out according to embodiment 1；
The BaNaP that will synthesize3O9Polycrystal powder and flux PbO in molar ratio 1:0.2 is mixed, and loads the mm of Φ 60
In the opening platinum crucible of × 60 mm, 720 °C are warming up to, 640 °C are cooled to after the h of constant temperature 60, obtain sodium phosphate barium and fluxing
The mixed molten liquid of agent；
The seed crystal platinum filament that the step b of embodiment 1 is obtained is tied up in the lower end of seed rod, seed crystal is imported away from earthenware from furnace roof portion aperture
At crucible about 1-2 cm, the min of constant temperature 25 is then immersed in below the liquid level of mixed molten liquid, fast cooling to 625 °C, with 15 rpm
Speed rotation seed crystal, lowered the temperature with the speed of 3 °C/d；
After after crystal growth stopping, by crystal lift-off liquid level, room temperature is down to the speed of 25 °C/h of temperature, then slowly from stove
Crystal is taken out in thorax, you can it is the sodium phosphate barium nonlinear optical crystal of 22 mm × 18 mm × 14 mm to obtain size.
Na in raw material2CO3Corresponding NaOH, NaNO can be used3、Na2C2O4Or CH3COONa is replaced, Ba (NO3)2Can be with
Use corresponding BaCO3、Ba(OH)2、BaC2O4、(CH3COO)2Ba is replaced, NH4H2PO4Corresponding NaH can be used2PO4、Na3PO4、
BaHPO4、Ba3(PO4)2Replace, can obtain sodium phosphate barium crystal.
Embodiment 3：
By taking reaction equation (3) as an example, but it is not limited to reaction equation (3)：
Using high temperature solid-state method, with reaction equation 2NaOH+2BaCO3 + 6NH4H2PO4 → 2BaNaP3O9 + 7H2O↑ +
2CO2↑ + 6NH3↑
Synthesis sodium phosphate barium (BaNaP3O9) compound, concrete operation step carried out according to embodiment 1；
The BaNaP that will synthesize3O9Polycrystal powder and flux PbO in molar ratio 1:0.25 is mixed, and loads the mm of Φ 60
In the opening platinum crucible of × 60 mm, 750 °C are warming up to, 630 °C are cooled to after the h of constant temperature 60, obtain sodium phosphate barium and fluxing
The mixed molten liquid of agent；
The seed crystal platinum filament that the step b of embodiment 1 is obtained is tied up in the lower end of seed rod, seed crystal is imported away from earthenware from furnace roof portion aperture
At crucible about 1-2 cm, the min of constant temperature 20 is then immersed in below the liquid level of mixed molten liquid, fast cooling to 625 °C, with 10 rpm
Speed rotation seed crystal, lowered the temperature with the speed of 1 °C/d；
After after crystal growth stopping, by crystal lift-off liquid level, room temperature is down to the speed of 30 °C/h of temperature, then slowly from stove
Crystal is taken out in thorax, you can it is the sodium phosphate barium nonlinear optical crystal of 25 mm × 19 mm × 16 mm to obtain size.
NaOH in raw material can use corresponding Na2CO3、NaNO3、Na2C2O4Or CH3COONa is replaced, BaCO3Phase can be used
The Ba (OH) for answering2、Ba(NO3)2、BaC2O4、(CH3COO)2Ba is replaced, NH4H2PO4Corresponding NaH can be used2PO4、Na3PO4、
BaHPO4、Ba3(PO4)2Replace, can obtain sodium phosphate barium crystal.
Embodiment 4：
By taking reaction equation (4) as an example, but it is not limited to reaction equation (4)：
Using high temperature solid-state method, with reaction equation 2NaOH+2Ba (NO3)2 + 6NH4H2PO4→ 2BaNaP3O9 + 7H2O↑ +
4NO2↑ + 6NH3↑
Synthesis sodium phosphate barium (BaNaP3O9) compound, concrete operation step carried out according to embodiment 1；
The BaNaP that will synthesize3O9Polycrystal powder and flux PbO in molar ratio 1:0.3 is mixed, and loads the mm of Φ 50
In the opening platinum crucible of × 50 mm, 730 °C are warming up to, 640 °C are cooled to after the h of constant temperature 60, obtain sodium phosphate barium and fluxing
The mixed molten liquid of agent；
The seed crystal platinum filament that the step b of embodiment 1 is obtained is tied up in the lower end of seed rod, seed crystal is imported away from earthenware from furnace roof portion aperture
At crucible about 1-2 cm, the min of constant temperature 20 is then immersed in below the liquid level of mixed molten liquid, fast cooling to 620 °C, with 15 rpm
Speed rotation seed crystal, lowered the temperature with the speed of 3 °C/d；
After after crystal growth stopping, by crystal lift-off liquid level, room temperature is down to the speed of 30 °C/h of temperature, then slowly from stove
Crystal is taken out in thorax, you can it is the sodium phosphate barium nonlinear optical crystal of 23 mm × 16 mm × 12 mm to obtain size.
NaOH in raw material can use corresponding Na2CO3、NaNO3、Na2C2O4Or CH3COONa is replaced, Ba (NO3)2Can be with
Use corresponding BaCO3、Ba(OH)2、BaC2O4、(CH3COO)2Ba is replaced, NH4H2PO4Corresponding NaH can be used2PO4、Na3PO4、
BaHPO4、Ba3(PO4)2Replace, can obtain sodium phosphate barium crystal.
Embodiment 5：
By taking reaction equation (5) as an example, but it is not limited to reaction equation (5)：
Using high temperature solid-state method, with reaction equation NaNO3 + BaCO3 + 3NH4H2PO4→BaNaP3O9 + NO2↑ + CO2↑ +
3NH3↑ + 3H2O↑
Synthesis sodium phosphate barium (BaNaP3O9) compound, concrete operation step carried out according to embodiment 1；
The BaNaP that will synthesize3O9Polycrystal powder and flux PbO in molar ratio 1:0.5 is mixed, and loads the mm of Φ 55
In the opening platinum crucible of × 55 mm, 700 °C are warming up to, 640 °C are cooled to after the h of constant temperature 50, obtain sodium phosphate barium and fluxing
The mixed molten liquid of agent；
The seed crystal platinum filament that the step b of embodiment 1 is obtained is tied up in the lower end of seed rod, seed crystal is imported away from earthenware from furnace roof portion aperture
At crucible about 1-2 cm, the min of constant temperature 10 is then immersed in below the liquid level of mixed molten liquid, fast cooling to 625 °C, with 30 rpm
Speed rotation seed crystal, lowered the temperature with the speed of 3 °C/d；
After after crystal growth stopping, by crystal lift-off liquid level, room temperature is down to the speed of 40 °C/h of temperature, then slowly from stove
Crystal is taken out in thorax, you can it is the sodium phosphate barium nonlinear optical crystal of 23 mm × 16 mm × 14 mm to obtain size.
NaNO in raw material3Corresponding Na can be used2CO3、NaOH、Na2C2O4Or CH3COONa is replaced, BaCO3Phase can be used
The Ba (OH) for answering2、Ba(NO3)2、BaC2O4、(CH3COO)2Ba is replaced, NH4H2PO4Corresponding NaH can be used2PO4、Na3PO4、
BaHPO4、Ba3(PO4)2Replace, can obtain sodium phosphate barium crystal.
Embodiment 6：
By taking reaction equation (6) as an example, but it is not limited to reaction equation (6)：
Using high temperature solid-state method, with reaction equation NaNO3+ Ba(NO3)2 + 3NH4H2PO4 → BaNaP3O9 + 3NO2↑ +
3NH3↑ + 3H2O↑
Synthesis sodium phosphate barium (BaNaP3O9) compound, concrete operation step carried out according to embodiment 1；
The BaNaP that will synthesize3O9Polycrystal powder and flux PbO in molar ratio 1:0.25 is mixed, and loads the mm of Φ 50
In the opening platinum crucible of × 50 mm, 700 °C are warming up to, 650 °C are cooled to after the h of constant temperature 80, obtain sodium phosphate barium and fluxing
The mixed molten liquid of agent；
The seed crystal platinum filament that the step b of embodiment 1 is obtained is tied up in the lower end of seed rod, seed crystal is imported away from earthenware from furnace roof portion aperture
At crucible about 1-2 cm, the min of constant temperature 20 is then immersed in below the liquid level of mixed molten liquid, fast cooling to 615 °C, with 20 rpm
Speed rotation seed crystal, lowered the temperature with the speed of 3 °C/d；
After after crystal growth stopping, by crystal lift-off liquid level, room temperature is down to the speed of 30 °C/h of temperature, then slowly from stove
Crystal is taken out in thorax, you can it is the sodium phosphate barium nonlinear optical crystal of 25 mm × 18 mm × 11 mm to obtain size.
NaNO in raw material3Corresponding Na can be used2CO3、NaOH、Na2C2O4Or CH3COONa is replaced, Ba (NO3)2Can be with
Use corresponding BaCO3、Ba(OH)2、BaC2O4、(CH3COO)2Ba is replaced, NH4H2PO4Corresponding NaH can be used2PO4、Na3PO4、
BaHPO4、Ba3(PO4)2Replace, can obtain sodium phosphate barium crystal.
Embodiment 7：
By taking reaction equation (7) as an example, but it is not limited to reaction equation (7)：
Using high temperature solid-state method, with reaction equation Na2C2O4 + 2BaCO3 + 6NH4H2PO4 → 2BaNaP3O9 + 4CO2↑ +
6NH3↑ + 6H2O↑
Synthesis sodium phosphate barium (BaNaP3O9) compound, concrete operation step carried out according to embodiment 1；
The BaNaP that will synthesize3O9Polycrystal powder and flux PbO in molar ratio 1:0.3 is mixed, and loads the mm of Φ 60
In the opening platinum crucible of × 60 mm, 740 °C are warming up to, 640 °C are cooled to after the h of constant temperature 60, obtain sodium phosphate barium and fluxing
The mixed molten liquid of agent；
The seed crystal platinum filament that the step b of embodiment 1 is obtained is tied up in the lower end of seed rod, seed crystal is imported away from earthenware from furnace roof portion aperture
At crucible about 1-2 cm, the min of constant temperature 25 is then immersed in below the liquid level of mixed molten liquid, fast cooling to 620 °C, with 25rpm's
Speed rotates seed crystal, is lowered the temperature with the speed of 3 °C/d；
After after crystal growth stopping, by crystal lift-off liquid level, room temperature is down to the speed of 10 °C/h of temperature, then slowly from stove
Crystal is taken out in thorax, you can it is the sodium phosphate barium nonlinear optical crystal of 23 mm × 17 mm × 14 mm to obtain size.
Na in raw material2C2O4Corresponding Na can be used2CO3、NaOH、NaNO3Or CH3COONa is replaced, BaCO3Phase can be used
The Ba (OH) for answering2、Ba(NO3)2、BaC2O4、(CH3COO)2Ba is replaced, NH4H2PO4Corresponding NaH can be used2PO4、Na3PO4、
BaHPO4、Ba3(PO4)2Replace, can obtain sodium phosphate barium crystal.
Embodiment 8：
By taking reaction equation (8) as an example, but it is not limited to reaction equation (8)：
Using high temperature solid-state method, with reaction equation 2CH3COONa + 2BaCO3 + 6NH4H2PO4 → 2BaNaP3O9 + 9H2O↑ +
6CO2↑ + 6NH3↑
Synthesis sodium phosphate barium (BaNaP3O9) compound, concrete operation step carried out according to embodiment 1；
The BaNaP that will synthesize3O9Polycrystal powder and flux PbO in molar ratio 1:0.2 is mixed, and loads the mm of Φ 50
In the opening platinum crucible of × 50 mm, 730 °C are warming up to, 630 °C are cooled to after the h of constant temperature 50, obtain sodium phosphate barium and fluxing
The mixed molten liquid of agent；
The seed crystal platinum filament that the step b of embodiment 1 is obtained is tied up in the lower end of seed rod, seed crystal is imported away from earthenware from furnace roof portion aperture
At crucible about 1-2 cm, the min of constant temperature 15 is then immersed in below the liquid level of mixed molten liquid, fast cooling to 625 °C, with 10rpm's
Speed rotates seed crystal, is lowered the temperature with the speed of 4 °C/d；
After after crystal growth stopping, by crystal lift-off liquid level, room temperature is down to the speed of 10 °C/h of temperature, then slowly from stove
Crystal is taken out in thorax, you can it is the sodium phosphate barium nonlinear optical crystal of 19 mm × 15 mm × 13 mm to obtain size.
CH in raw material3COONa can use corresponding Na2CO3、NaOH、NaNO3Or Na2C2O4Replace, BaCO3Phase can be used
The Ba (OH) for answering2、Ba(NO3)2、BaC2O4、(CH3COO)2Ba is replaced, NH4H2PO4Corresponding NaH can be used2PO4、Na3PO4、
BaHPO4、Ba3(PO4)2Replace, can obtain sodium phosphate barium crystal.
Claims (4)
1. a kind of preparation method of sodium phosphate barium nonlinear optical crystal, it is characterised in that the crystal molecule formula is：BaNaP3O9,
Space group isP212121, cell parameter is：a =5.7765 (14),b =11.036 (3),c =12.257 (3),Z
=4,V = 781.4(3) Å3, it is that concrete operations are by following with 25 mm × 19 mm × 16 mm large-sized monocrystalline
Step is carried out：
A, sodium phosphate barium polycrystal powder obtained in high temperature solid-state method and flux PbO in molar ratio 1 will be used:0.1-5 is mixed
Close, be fitted into the opening platinum crucible of mm × 60 mm of Φ 60, be heated to 700-750 °C of temperature, constant temperature 1-100 h are obtained
The mixed molten liquid of sodium phosphate barium and flux；
B, will be tied with the corundum bar of platinum filament be put into step a preparation mixed molten liquid in, under immersed in liquid level, fast cooling to 630-
680 °C, then with the speed of 5-30 °C/d of temperature by mixed molten liquid slow cooling, the crystal on seed rod to be gathered in grows to one
When being sized, by crystal lift-off liquid level, room temperature is down to the speed of 5-50 °C/h of temperature, obtains small crystals as seed crystal；
C, mixed molten liquid is prepared again：It is in molar ratio 1 by sodium phosphate barium polycrystal powder and flux PbO:0.1-5 is mixed
Close, be fitted into the opening platinum crucible of mm × 60 mm of Φ 60, be heated to 700-750 °C, constant temperature 1-100 h, then drop
Temperature obtains the mixed molten liquid of sodium phosphate barium and flux, then the seed crystal platinum filament that step b is obtained is tied up in seed to 630-680 °C
The lower end of crystalline style, imports at crucible about 1-2 cm seed crystal from furnace roof portion aperture, constant temperature 5-30 min, is then immersed in mixing molten
Below liquid liquid level, fast cooling rotates seed crystal to 615-625 °C with the speed of 1-30 rpm, slow with the speed of 1-5 °C/d
Cooling；
D, after crystal growth stopping after, by crystal lift-off liquid level, room temperature is down to the speed of 5-50 °C/h of temperature, then slowly
Crystal is taken out from burner hearth, you can obtain sodium phosphate barium nonlinear optical crystal.
2. method according to claim 1, it is characterised in that the compound containing sodium is Na in step a sodium phosphate bariums2CO3、
NaOH、NaNO3、Na2C2O4Or CH3COONa；The compound of baric is BaCO3、Ba(OH)2、Ba(NO3)2、BaC2O4、
(CH3COO)2Ba；Phosphorus-containing compound is NaH2PO4、Na3PO4、 BaHPO4、Ba3(PO4)2、NH4H2PO4。
3. method according to claim 1, it is characterised in that sodium phosphate barium and the mol ratio of flux PbO are 1 in step a
: 0.1-5。
4. method according to claim 1, it is characterised in that the sodium phosphate barium non-linear optical crystal obtained by the method
Body is used as the purposes for preparing times frequency generator.
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|---|---|---|---|---|
| CN109056065A (en) * | 2018-09-06 | 2018-12-21 | 新疆大学 | MZnPO4The preparation method and purposes of (M=Li, K) nonlinear optical crystal |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6391229B1 (en) * | 1999-01-07 | 2002-05-21 | Mitsubishi Materials Corporation | Borate crystal, growth method of the same and laser equipment using the same |
| CN102912433A (en) * | 2012-10-26 | 2013-02-06 | 中国科学院福建物质结构研究所 | Ba3P3O10Br single crystal and preparation method thereof |
| CN105133016A (en) * | 2015-10-09 | 2015-12-09 | 新疆大学 | Preparation method and application of lithium vanadate nonlinear optical crystal |
-
2016
- 2016-11-22 CN CN201611025909.8A patent/CN106757345B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6391229B1 (en) * | 1999-01-07 | 2002-05-21 | Mitsubishi Materials Corporation | Borate crystal, growth method of the same and laser equipment using the same |
| CN102912433A (en) * | 2012-10-26 | 2013-02-06 | 中国科学院福建物质结构研究所 | Ba3P3O10Br single crystal and preparation method thereof |
| CN105133016A (en) * | 2015-10-09 | 2015-12-09 | 新疆大学 | Preparation method and application of lithium vanadate nonlinear optical crystal |
Non-Patent Citations (3)
| Title |
|---|
| （英）潘普林（B.R.PAMPLIN）: "《晶体生长》", 31 December 1981, 中国建筑工业出版社 * |
| MARTIN C. ET AL.: "Crystal structure of the trimetaphosphate of barium and sodium: BaNaP3O9", 《ACTA CRYST.》 * |
| 赵连城等编: "《信息功能材料学》", 31 July 2005, 哈尔滨工业大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109056065A (en) * | 2018-09-06 | 2018-12-21 | 新疆大学 | MZnPO4The preparation method and purposes of (M=Li, K) nonlinear optical crystal |
| CN109056065B (en) * | 2018-09-06 | 2021-03-30 | 新疆大学 | Preparation method and application of MZnPO4(M = Li, K) nonlinear optical crystal |
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