CN103361726B - Compound sodium phosphate lithium and sodium phosphate lithium non-linear optic crystal and preparation method and purposes - Google Patents

Compound sodium phosphate lithium and sodium phosphate lithium non-linear optic crystal and preparation method and purposes Download PDF

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CN103361726B
CN103361726B CN201210081834.0A CN201210081834A CN103361726B CN 103361726 B CN103361726 B CN 103361726B CN 201210081834 A CN201210081834 A CN 201210081834A CN 103361726 B CN103361726 B CN 103361726B
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sodium phosphate
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phosphate lithium
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CN103361726A (en
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潘世烈
史云晶
董孝宇
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Abstract

The present invention relates to compound sodium phosphate lithium and sodium phosphate lithium non-linear optic crystal and preparation method and purposes, this compound is same composition melting compound, and chemical formula is LiNa 3p 2o 7, molecular weight is 249.85; The chemical formula of sodium phosphate lithium non-linear optic crystal is LiNa 3p 2o 7, molecular weight is 249.85, and spacer is C222 1, unit cell parameters is a=5.4966 (2), b=9.1365 (4), c=12.2764 (5), Z=4. the powder SHG effect of this compound is equivalent to 0.2 times of KDP, transmission region 300nm to 2600nm, adopts solid reaction process synthetic compound and melt method for crystal growth.Method of the present invention is simple to operate, and cost is low; Prepared crystal not deliquescence in atmosphere, good mechanical property, not easily broken, physico-chemical property is stablized, and easily processes, and is suitable for making device for non-linear optical.

Description

Compound sodium phosphate lithium and sodium phosphate lithium non-linear optic crystal and preparation method and purposes
Technical field
The present invention relates to a kind of with composition melting compound sodium phosphate lithium and sodium phosphate lithium non-linear optic crystal and preparation method and purposes.
Background technology
Nonlinear optical material crystal is widely used in laser frequency conversion, four-wave mixing, light beam turn to, image multiplication, optical information processing, optical storage, optical-fibre communications, underwater communication, the research field such as laser countermeasure (s) and nucleosynthesis.Along with the development of laser technology, find and can be applied to the focus that the ultraviolet even laser frequency doubling crystal in deep ultraviolet region are scientific circles' research non-linear optic crystals always.
In recent decades, a large amount of borates, phosphoric acid salt are widely studied, and have emerged large quantities of non-linear compound crystalline material with excellent frequency-doubled effect, as BBO, LBO, KBBF, KDP, KTP, DKDP etc.As everyone knows, non-centrosymmetrical structure may present nonlinear optical property.At present, a lot of non-centrosymmetrical phosphoric acid salt is had to be found, such as, K (D xh 1-x) 2pO 4, NH 4h 2pO, K xrb 1-xtiOPO 4, KNd (PO 3) 4deng.
P abundant in phosphoric acid salt is mainly come to the research interest of metal phosphate no mgroup, as: PO 4, P 2o 7, P 3o 10, P 3o 9, P 4o 12and P 6o 18.Existing a lot of about phosphatic report, as: Li 6cuB 4o 10, Li 2cu 5(PO 4) 4, Ca 3(PO 4) 2, KMgFe (PO 4) 2, KCuFe (PO 4) 2deng.Therefore, to the further further investigation of phosphate system, there is important actual application value.
According to current inorganic nonlinear optical crystal Materials situation, novel inorganic non-linear optic crystal is not only required to have large Clock Multiplier Factor, but also require that its comprehensive performance parameter is good, be easy to generate high quality and large size body block crystal, this just needs to carry out a large amount of system and deep research work simultaneously.
Summary of the invention:
The object of the invention is that provide a kind of compound sodium phosphate lithium, this compound is same composition melting compound, and chemical formula is LiNa in order to solve the needs being applied to the nonlinear optical material of all-solid state laser system 3p 2o 7, molecular weight is 249.85.
Another object of the present invention is to provide a kind of sodium phosphate lithium non-linear optic crystal, and this crystal is same composition melting compound, and chemical formula is LiNa 3p 2o 7, molecular weight is 249.85, and spacer is C222 1, unit cell parameters is a=5.4966 (2), b=9.1365 (4), c=12.2764 (5), Z=4.
Further object of the present invention is to provide the preparation method adopting solid reaction process synthetic compound and melt method for growing sodium phosphate lithium non-linear optic crystal.
Another object of the present invention is to provide a kind of purposes of sodium phosphate lithium non-linear optic crystal.
A kind of compound sodium phosphate lithium of the present invention, is characterized in that this compound is that chemical formula is: LiNa with composition melting compound 3p 2o 7, molecular weight is 249.85, adopts solid reaction process synthetic compound.
A kind of compound phosphoric acid salt sodium lithium non-linear optic crystal, chemical formula is LiNa 3p 2o 7, molecular weight is 249.85, and spacer is C222 1, unit cell parameters is a=5.4966 (2), b=9.1365 (4), c=12.2764 (5), Z=4.
The preparation method of described sodium phosphate lithium non-linear optic crystal, adopt solid reaction process synthetic compound and its crystal of melt method for growing, concrete operation step is undertaken by following:
A, will containing sodium, in molar ratio containing lithium and P contained compound take put into mortar at 3: 1: 2, mixing is also carefully ground, load corundum crucible, put into retort furnace, slowly be warming up to 200 DEG C, constant temperature 5 hours, be cooled to grinding at room temperature even, slowly be warming up to 400 DEG C, gas is drained only, take out crucible after cooling, by sample grinding evenly, compacting, be placed in crucible again, retort furnace is warming up to 540 DEG C, sample took out after 72 hours by constant temperature, put into mortar to smash grinding to pieces and namely obtain sodium phosphate lithium compound single-phase polycrystalline powder, again X-ray analysis is carried out to this polycrystal powder, gained X-ray spectrogram and finished product monocrystalline are pulverized last LiNa 3p 2o 7monocrystalline last X-ray spectrogram of pulverizing is consistent,
B, the polycrystal powder obtained by step a grind evenly, temperature 700 DEG C is heated to the temperature rise rate of temperature 20-30 DEG C/h, constant temperature 20-50 hour, then be cooled to temperature 630 DEG C to obtain melt, enter seed rod in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, and then slowly drops to temperature 620 DEG C with the speed of temperature 0.5-5 DEG C/h, then seed rod is proposed liquid level, be down to room temperature with the speed of temperature 10-50 DEG C/h, obtain sodium phosphate lithium seed crystal;
C, sodium phosphate lithium melt is prepared again: the polycrystal powder grinding obtained by step a evenly by step b, temperature 700 DEG C is heated to the temperature rise rate of temperature 20-30 DEG C/h, constant temperature 20-50 hour, temperature 630 DEG C is cooled to obtain melt again, again the seed crystal that step b obtains is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 5-60 minute, then declining makes seed crystal contact with bath surface or stretch in melt, be down to temperature 625 DEG C, with the rotating speed rotary seed crystal rod of 20-50rpm, with the speed slow cooling to 620 DEG C of temperature 0.5-2 DEG C/d, reach crystal growth desired size,
D, arrive after required yardstick until single crystal growing, by crystal lift-off bath surface, be down to room temperature with the speed of temperature 20-50 DEG C/h, then crystal taken out from burner hearth, sodium phosphate crystalline lithium can be obtained.
Compound sodium phosphate lithium LiNa described in step a 3p 2o 7in be Na containing the compound of sodium 2cO 3, NaNO 3, Na 2o or NaOH; Compound containing lithium is Li 2cO 3or LiF; P contained compound is NH 4h 2pO 4.
The purposes of described sodium phosphate lithium non-linear optic crystal, this crystal is for the preparation of doubly frequency generator, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
Compound sodium phosphate lithium of the present invention, this compound is the compound of same composition melting, and chemical formula is LiNa 3p 2o 7, molecular weight is 249.85; Sodium phosphate lithium non-linear optic crystal is the compound of same composition melting, and chemical formula is LiNa 3p 2o 7, molecular weight is 249.85, and spacer is C222 1, unit cell parameters is a=5.4966 (2), b=9.1365 (4), c=12.2764 (5), Z=4, its powder SHG effect is about the KDP of 0.2 times; Transmission region 300nm-2600nm, the advantages such as adopt melt method for crystal growth, prepare the sodium phosphate lithium non-linear optic crystal with centimeter-scale, the method has simple to operate, and cost is low, and good mechanical property is not easily broken, and physico-chemical property is stable.
The present invention in principle, adopts general chemical synthesis process can prepare sodium phosphate lithium (LiNa 3p 2o 7) polycrystal raw material, preferred solid reaction process, that is:, after being mixed by the raw materials of compound containing Na, Li and P mol ratio being 3: 1: 2, solid state reaction is carried out in heating, and can obtain chemical formula is LiNa 3p 2o 7compound.
Prepare sodium phosphate lithium (LiNa 3p 2o 7) chemical equation of compound:
(1)Na 2CO 3+Li 2CO 3+NH 4H 2PO 4→LiNa 3P 2O 7+H 2O↑+CO 2↑+NH 3↑
(2)NaNO 3+Li 2CO 3+NH 4H 2PO 4→LiNa 3P 2O 7+NH 3↑+CO 2↑+NO 2↑+H 2O↑
(3)Na 2O+Li 2CO 3+NH 4H 2PO 4→LiNa 3P 2O 7+CO 2↑+NH 3↑+H 2O↑
(4)NaOH+Li 2CO 3+NH 4H 2PO 4→LiNa 3P 2O 7+CO 2↑+H 2O↑+NH 3↑
(5)Na 2CO 3+LiF+NH 4H 2PO 4→LiNa 3P 2O 7+H 2O↑+CO 2↑+NH 3↑+HF↑
(6)NaNO 3+LiF+NH 4H 2PO 4→LiNa 3P 2O 7+NH 3↑+NO 2↑+H 2O↑+HF↑
(7)Na 2O+LiF+NH 4H 2PO 4→LiNa 3P 2O 7+NH 3↑+H 2O↑+HF↑
(8)NaOH+LiF+NH 4H 2PO 4→LiNa 3P 2O 7+H 2O↑+NH 3↑+HF↑
Contain sodium in the present invention, commercially available reagent and raw material can be adopted containing lithium and P contained compound.
The preparation method of described compound sodium phosphate lithium non-linear optic crystal, adopts melt method for crystal growth.
Large-sized sodium phosphate lithium (LiNa of the present invention 3p 2o 7) non-linear optic crystal can make device for non-linear optical, comprise and make times frequency generator, upper or lower frequency transmodulator and optical parametric oscillator.Described comprising with the nonlinear device that sodium phosphate lithium non-linear optic crystal makes produces through at least a branch of incident fundamental wave the coherent light that at least a branch of frequency is different from incident light.
Described sodium phosphate lithium non-linear optic crystal to optical manufacturing precision without particular requirement.
Accompanying drawing explanation
Fig. 1 is the powder x-ray diffraction collection of illustrative plates of the compounds of this invention sodium phosphate lithium.
Fig. 2 is the structure iron of sodium phosphate crystalline lithium of the present invention.
Fig. 3 is the fundamental diagram of the device for non-linear optical that sodium phosphate crystalline lithium of the present invention makes, and wherein: 1 is laser apparatus, 2 is complete poly-mirror, and 3 for injecting crystal, and 4 is beam splitting prism, and 5 is filter plate.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail:
Embodiment 1:
Synthesis LiNa 3p 2o 7compound:
Adopt solid reaction process to sinter at high temperature 540 DEG C, its chemical equation is: Na 2cO 3+ Li 2cO 3+ NH 4h 2pO 4→ LiNa 3p 2o 7+ H 2o ↑+CO 2↑+NH 3↑
Will containing Na, containing Li, in molar ratio containing P-compound take put into mortar at 3: 1: 2, mixing is also carefully ground, load corundum crucible, put into retort furnace, slowly be warming up to 200 DEG C, constant temperature 5 hours, be cooled to grinding at room temperature even, slowly be warming up to 400 DEG C, gas is drained only as far as possible, take out crucible after cooling, by sample grinding evenly, be placed in crucible again, retort furnace is warming up to 540 DEG C, sample took out after 72 hours by constant temperature, put into mortar to smash grinding to pieces and namely obtain sodium phosphate lithium compound single-phase polycrystalline powder, again X-ray analysis is carried out to this polycrystal powder, gained X-ray spectrogram and finished product LiNa 3p 2o 7monocrystalline last X-ray spectrogram of pulverizing is consistent,
Growing large-size sodium phosphate crystalline lithium in the melt:
By the compound sodium phosphate lithium LiNa of synthesis 3p 2o 7single-phase polycrystalline powder loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 700 DEG C are heated to the temperature rise rate of temperature 30 DEG C/h, constant temperature 30 hours, be cooled to temperature 630 DEG C again, obtain sodium phosphate lithium melt, seed rod is entered in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, and then slowly drops to temperature 620 DEG C with the speed of temperature 0.5 DEG C/h, seed rod is proposed liquid level, be down to room temperature with the speed of temperature 10 DEG C/h, sodium phosphate lithium seed crystal can be obtained;
And then prepare sodium phosphate lithium melt: by the compound sodium phosphate lithium LiNa of synthesis 3p 2o 7single-phase polycrystalline powder loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 700 DEG C are heated to the temperature rise rate of temperature 30 DEG C/h, constant temperature 30 hours, be cooled to temperature 630 DEG C again, obtain sodium phosphate lithium melt, the seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 5 minutes, then declining makes seed crystal contact with sodium phosphate lithium bath surface, with the rotating speed rotary seed crystal rod of 20rpm, with the speed slow cooling of temperature 1 DEG C/d to the temperature 620 DEG C of crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off molten surface, be down to room temperature with the speed of temperature 30 DEG C/h, then crystal is taken out from burner hearth, 20mm × 12mm × 8mm sodium phosphate lithium monocrystalline can be obtained.
Na in raw material 2cO 3can be replaced NaNO 3, Na 2o or NaOH; Li 2cO 3can be replaced LiF.
Embodiment 2:
By reaction formula NaNO 3+ Li 2cO 3+ NH 4h 2pO 4→ LiNa 3p 2o 7+ NH 3↑+CO 2↑+NO 2↑+H 2o ↑ synthesis LiNa 3p 2o 7compound, concrete operation step carries out according to embodiment 1;
By the sodium phosphate lithium LiNa of synthesis 3p 2o 7compound single-phase polycrystal powder loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 700 DEG C are heated with the temperature rise rate of temperature 5 DEG C/h, constant temperature 35 hours, be cooled to 630 DEG C again, obtain sodium phosphate lithium melt, seed rod is entered in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, and then slowly drops to temperature 620 DEG C with the speed of temperature 0.5 DEG C/h, seed rod is proposed liquid level, be down to room temperature with the speed of temperature 10 DEG C/h, sodium phosphate lithium seed crystal can be obtained;
And then prepare sodium phosphate lithium melt: by the compound sodium phosphate lithium LiNa of synthesis 3p 2o 7single-phase polycrystalline powder loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 700 DEG C are heated to the temperature rise rate of temperature 30 DEG C/h, constant temperature 30 hours, be cooled to temperature 630 DEG C again, obtain sodium phosphate lithium melt, the seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 20 minutes, then declining makes seed crystal contact with sodium phosphate lithium bath surface, with the rotating speed rotary seed crystal rod of 20rpm, with the speed slow cooling of temperature 0.5 DEG C/d to the temperature 620 DEG C of crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off molten surface, be down to room temperature with the speed of temperature 20 DEG C/h, then crystal taken out from burner hearth, 15mm × 10mm × 7mm sodium phosphate lithium monocrystalline can be obtained.
NaNO in raw material 3can be replaced Na 2cO 3, Na 2o or NaOH; Li 2cO 3can be replaced LiF.
Embodiment 3:
By reaction formula Na 2o+Li 2cO 3+ NH 4h 2pO 4→ LiNa 3p 2o 7+ CO 2↑+NH 3↑+H 2o ↑ synthesis LiNa 3p 2o 7compound, concrete operation step carries out according to embodiment 1;
By the compound sodium phosphate lithium LiNa of synthesis 3p 2o 7single-phase polycrystalline powder loads in the opening platinum crucible of Φ 80mm × 80mm, puts into crystal growing furnace, is heated to 700 DEG C with the temperature rise rate of temperature 25 DEG C/h, constant temperature 20 hours, be cooled to 630 DEG C again, obtain sodium phosphate lithium melt, fast, enter seed rod in melt, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, and slowly drops to 620 DEG C, seed rod is proposed liquid level with the speed of temperature 1.5 DEG C/h, be down to room temperature with the speed of temperature 10 DEG C/h, sodium phosphate lithium seed crystal can be obtained;
And then prepare sodium phosphate lithium melt: by the compound sodium phosphate lithium LiNa of synthesis 3p 2o 7single-phase polycrystalline powder loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 700 DEG C are heated to the temperature rise rate of temperature 30 DEG C/h, constant temperature 30 hours, be cooled to temperature 630 DEG C again, obtain sodium phosphate lithium melt, the seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 10 minutes, then declining makes seed crystal contact with sodium phosphate lithium bath surface, with the rotating speed rotary seed crystal rod of 40rpm, with the speed slow cooling of temperature 1.5 DEG C/d to the temperature 620 DEG C of crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off molten surface, be down to room temperature with the speed of temperature 25 DEG C/h, then crystal taken out from burner hearth, 17mm × 14mm × 11mm sodium phosphate lithium monocrystalline can be obtained.
Na in raw material 2o can be replaced Na 2cO 3, NaOH or NaNO 3; Li 2cO 3can be replaced LiF.
Embodiment 4:
By reaction formula NaOH+Li 2cO 3+ NH 4h 2pO 4→ LiNa 3p 2o 7+ CO 2↑+H 2o ↑+NH 3↑ synthesis LiNa 3p 2o 7compound, concrete operation step carries out according to embodiment 1;
By the compound sodium phosphate lithium LiNa of synthesis 3p 2o 7single-phase polycrystalline powder, loads in the opening platinum crucible of Φ 80mm × 80mm, puts into crystal growing furnace, be heated to 700 DEG C with the temperature rise rate of temperature 23 DEG C/h, constant temperature 50 hours, then be cooled to 630 DEG C, obtain sodium phosphate lithium liquation, enter seed rod in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, 620 DEG C are slowly dropped to the speed of temperature 0.5 DEG C/h, seed rod is proposed liquid level, is down to room temperature with the speed of temperature 20 DEG C/h, sodium phosphate lithium seed crystal can be obtained;
And then prepare sodium phosphate lithium melt: by the compound sodium phosphate lithium LiNa of synthesis 3p 2o 7single-phase polycrystalline powder loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 700 DEG C are heated to the temperature rise rate of temperature 30 DEG C/h, constant temperature 30 hours, be cooled to temperature 630 DEG C again, obtain sodium phosphate lithium melt, the seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 25 minutes, then declining makes seed crystal contact with sodium phosphate lithium bath surface, with the rotating speed rotary seed crystal rod of 30rpm, with the speed slow cooling of temperature 2 DEG C/d to the temperature 620 DEG C of crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off molten surface, be down to room temperature with the speed of temperature 30 DEG C/h, then crystal taken out from burner hearth, 12mm × 10mm × 6mm sodium phosphate lithium monocrystalline can be obtained.
NaOH in raw material can be replaced Na 2cO 3, NaNO 3or Na 2o; Li 2cO 3can be replaced LiF.
Embodiment 5:
By reaction formula Na 2cO 3+ LiF+NH 4h 2pO 4→ LiNa 3p 2o 7+ H 2o ↑+CO 2↑+NH 3↑+HF ↑ synthesis LiNa 3p 2o 7compound, concrete operation step carries out according to embodiment 1;
By the sodium phosphate lithium LiNa of synthesis 3p 2o 7compound single-phase polycrystal powder, loads in the opening platinum crucible of Φ 80mm × 80mm, puts into crystal growing furnace, be heated to 700 DEG C with the temperature rise rate of temperature 30 DEG C/h, constant temperature 40 hours, then be cooled to 630 DEG C, obtain sodium phosphate lithium melt, enter seed rod in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, with the speed slow cooling to 620 DEG C of temperature 5 DEG C/h, seed rod is proposed liquid level, then is down to room temperature with the speed of temperature 20 DEG C/h, sodium phosphate lithium seed crystal can be obtained;
And then prepare sodium phosphate lithium melt: by the compound sodium phosphate lithium LiNa of synthesis 3p 2o 7single-phase polycrystalline powder loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 700 DEG C are heated to the temperature rise rate of temperature 30 DEG C/h, constant temperature 30 hours, be cooled to temperature 630 DEG C again, obtain sodium phosphate lithium melt, the seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 5 minutes, then stretch into as in melt, with the rotating speed rotary seed crystal rod of 50rpm, with the speed slow cooling of temperature 0.5 DEG C/d to the temperature 620 DEG C of crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off molten surface, be down to room temperature with the speed of temperature 35 DEG C/h, crystal is taken out from burner hearth, 11mm × 9mm × 8mm sodium phosphate lithium monocrystalline can be obtained.
Na in raw material 2cO 3can be replaced NaNO 3, Na 2o or NaOH; LiF can be replaced Li 2cO 3.
Embodiment 6:
By reaction formula NaNO 3+ LiF+NH 4h 2pO 4→ LiNa 3p 2o 7+ NH 3↑+NO 2↑+H 2o ↑+HF ↑ synthesis LiNa 3p 2o 7compound, concrete operation step carries out according to embodiment 1;
By the sodium phosphate lithium LiNa of synthesis 3p 2o 7compound single-phase polycrystal powder, load in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 700 DEG C are heated to the temperature rise rate of temperature 30 DEG C/h, constant temperature 50 hours, be cooled to temperature 630 DEG C again, obtain sodium phosphate melt, enter seed rod in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, temperature 620 DEG C is slowly dropped to the speed of temperature 1.5 DEG C/h, seed rod is proposed liquid level, is down to room temperature with the speed of temperature 35 DEG C/h, sodium phosphate lithium seed crystal can be obtained;
And then prepare sodium phosphate lithium melt: by the compound sodium phosphate lithium LiNa of synthesis 3p 2o 7single-phase polycrystalline powder loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 700 DEG C are heated to the temperature rise rate of temperature 30 DEG C/h, constant temperature 30 hours, be cooled to temperature 630 DEG C again, obtain sodium phosphate lithium melt, the seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 45 minutes, then decline stretch into as in melt with the rotating speed rotary seed crystal rod of 50rpm, with the speed slow cooling of temperature 2 DEG C/d to the temperature 620 DEG C of crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off bath surface, be down to room temperature with the speed of temperature 35 DEG C/h, then crystal taken out from burner hearth, 14mm × 11mm × 7mm sodium phosphate lithium monocrystalline can be obtained.
NaNO in raw material 3can be replaced Na 2cO 3, Na 2o or NaOH; LiF can be replaced Li 2cO 3.
Embodiment 7:
By reaction formula Na 2o+LiF+NH 4h 2pO 4→ LiNa 3p 2o 7+ NH 3↑+H 2o ↑+HF ↑ synthesis LiNa 3p 2o 7compound, concrete operation step carries out according to embodiment 1;
By the sodium phosphate lithium LiNa of synthesis 3p 2o 7compound single-phase polycrystal powder, load in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 700 DEG C are heated to the temperature rise rate of temperature 20 DEG C/h, constant temperature 30 hours, be cooled to 630 DEG C again, obtain sodium phosphate lithium melt, enter seed rod in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, temperature 620 DEG C is slowly dropped to the speed of temperature 2 DEG C/h, seed rod is proposed liquid level, is down to room temperature with the speed of temperature 40 DEG C/h, sodium phosphate lithium seed crystal can be obtained;
And then prepare sodium phosphate lithium melt: by the compound sodium phosphate lithium LiNa of synthesis 3p 2o 7single-phase polycrystalline powder loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 700 DEG C are heated to the temperature rise rate of temperature 30 DEG C/h, constant temperature 30 hours, be cooled to temperature 630 DEG C again, obtain sodium phosphate lithium melt, the seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 60 minutes, then declining makes seed crystal contact with sodium phosphate lithium bath surface, with the rotating speed rotary seed crystal rod of 30rpm, with the speed slow cooling of temperature 0.5 DEG C/d to the temperature 620 DEG C of crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off bath surface, be down to room temperature with the speed of temperature 40 DEG C/h, then crystal taken out from burner hearth, 17mm × 11mm × 10mm sodium phosphate lithium monocrystalline can be obtained.
Na in raw material 2o can be replaced Na 2cO 3, NaNO 3or NaOH; LiF can be replaced Li 2cO 3.
Embodiment 8:
By reaction formula NaOH+LiF+NH 4h 2pO 4→ LiNa 3p 2o 7+ H 2o ↑+NH 3↑+HF ↑ synthesis LiNa 3p 2o 7compound, concrete operation step carries out according to embodiment 1;
By the sodium phosphate lithium LiNa of synthesis 3p 2o 7compound single-phase polycrystal powder, load in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 700 DEG C are heated to the temperature rise rate of temperature 50 C/h, constant temperature 30 hours, be cooled to temperature 630 DEG C again, obtain sodium phosphate lithium melt, enter seed rod in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, temperature 620 DEG C is slowly dropped to the speed of temperature 1.5 DEG C/h, seed rod is proposed liquid level, is down to room temperature with the speed of temperature 35 DEG C/h, sodium phosphate lithium seed crystal can be obtained;
And then prepare sodium phosphate lithium melt: by the compound sodium phosphate lithium LiNa of synthesis 3p 2o 7single-phase polycrystalline powder loads in the opening platinum crucible of Φ 80mm × 80mm, put into crystal growing furnace, 700 DEG C are heated to the temperature rise rate of temperature 30 DEG C/h, constant temperature 30 hours, be cooled to temperature 630 DEG C again, obtain sodium phosphate lithium melt, the seed crystal of acquisition is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 50 minutes, then declining makes seed crystal contact with sodium phosphate lithium bath surface, with the rotating speed rotary seed crystal rod of 50rpm, with the speed slow cooling of temperature 1.5 DEG C/d to the temperature 620 DEG C of crystal desired size;
Arrive after required yardstick until single crystal growing, by crystal lift-off bath surface, be down to room temperature with the speed of temperature 30 DEG C/h, then crystal taken out from burner hearth, 15mm × 12mm × 9mm sodium phosphate lithium monocrystalline can be obtained.
NaOH in raw material can be replaced Na 2cO 3, NaNO 3or Na 2o; LiF can be replaced Li 2cO 3.
Embodiment 9:
By any crystal of gained in example 1-8, by being placed in shown in accompanying drawing on the position of 3, at room temperature, export with adjusting the 1064nm of QNd:YAG laser apparatus and make light source, observe obvious 532nm frequency doubling green light and export, output intensity is about 0.2 times of equal conditions KDP; Sending wavelength with adjusting QNd:YAG laser apparatus 1 is that the infrared beam of 1064nm injects LiNa through convex lens 2 3p 2o 7crystal 3, produce the green frequency doubled light that wavelength is 532nm, outgoing beam 4 is the infrared light of 1064nm and the green glow of 532nm containing wavelength, and filter plate 5 elimination infrared light composition, obtains the green laser that wavelength is 532nm.

Claims (5)

1. a compound sodium phosphate lithium, it is characterized in that this compound is congruent compound, chemical formula is: LiNa 3p 2o 7, molecular weight is 249.85, adopts solid reaction process synthetic compound.
2. a compound phosphoric acid salt sodium lithium non-linear optic crystal, it is characterized in that this crystal is the compound of congruent melting, chemical formula is LiNa 3p 2o 7, molecular weight is 249.85, and spacer is C222 1, unit cell parameters is z=4,
3. the preparation method of sodium phosphate lithium non-linear optic crystal according to claim 2, it is characterized in that adopting solid reaction process synthetic compound and its crystal of melt method for growing, concrete operation step is undertaken by following:
A, will containing sodium, in molar ratio containing lithium and P contained compound take put into mortar at 3: 1: 2, mixing is also carefully ground, load corundum crucible, put into retort furnace, slowly be warming up to 200 DEG C, constant temperature 5 hours, be cooled to grinding at room temperature even, slowly be warming up to 400 DEG C, gas is drained only, take out crucible after cooling, by sample grinding evenly, compacting, be placed in crucible again, retort furnace is warming up to 540 DEG C, sample took out after 72 hours by constant temperature, put into mortar to smash grinding to pieces and namely obtain sodium phosphate lithium compound single-phase polycrystalline powder, again X-ray analysis is carried out to this polycrystal powder, gained X-ray spectrogram and finished product LiNa 3p 2o 7monocrystalline last X-ray spectrogram of pulverizing is consistent,
B, the polycrystal powder obtained by step a grind evenly, temperature 700 DEG C is heated to the temperature rise rate of temperature 20-30 DEG C/h, constant temperature 20-50 hour, then be cooled to temperature 630 DEG C to obtain melt, enter seed rod in melt fast, treat that it produces drift crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, and then slowly drops to temperature 620 DEG C with the speed of temperature 0.5-5 DEG C/h, then seed rod is proposed liquid level, be down to room temperature with the speed of temperature 10-50 DEG C/h, obtain sodium phosphate lithium seed crystal;
C, sodium phosphate lithium melt is prepared again: the polycrystal powder grinding obtained by step a evenly by step b, temperature 700 DEG C is heated to the temperature rise rate of temperature 20-30 DEG C/h, constant temperature 20-50 hour, temperature 630 DEG C is cooled to obtain melt again, again the seed crystal that step b obtains is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 5-60 minute, then declining makes seed crystal contact with bath surface or stretch in melt, with the rotating speed rotary seed crystal rod of 20-50rpm, with the speed slow cooling to 620 DEG C of temperature 0.5-2 DEG C/d, reach crystal growth desired size,
D, arrive after required yardstick until single crystal growing, by crystal lift-off bath surface, be down to room temperature with the speed of temperature 20-50 DEG C/h, then crystal taken out from burner hearth, sodium phosphate crystalline lithium can be obtained.
4. method according to claim 3, is characterized in that compound sodium phosphate lithium LiNa described in step a 3p 2o 7in be Na containing the compound of sodium 2cO 3, NaNO 3, Na 2o or NaOH; Compound containing lithium is Li 2cO 3or LiF; P contained compound is NH 4h 2pO 4.
5. the purposes of sodium phosphate lithium non-linear optic crystal according to claim 2, is characterized in that this crystal is for the preparation of doubly frequency generator, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105568381A (en) * 2014-10-15 2016-05-11 中国科学院新疆理化技术研究所 Yttrium phosphate double-refraction crystal and growing method and application thereof
CN106192005B (en) * 2015-05-08 2018-03-20 中国科学院新疆理化技术研究所 Compound lithium phosphate caesium nonlinear optical crystal and preparation method and purposes
CN106192003B (en) * 2015-05-08 2018-03-20 中国科学院新疆理化技术研究所 Compound lithium phosphate rubidium nonlinear optical crystal and preparation method and purposes
CN105839185B (en) * 2016-05-16 2018-04-10 中国科学院福建物质结构研究所 Cs2LiPO4Compound, Cs2LiPO4Nonlinear optical crystal and its preparation method and purposes
CN106495121B (en) * 2016-10-14 2018-08-28 中国科学院福建物质结构研究所 CsLiCdP2O7Compound, CsLiCdP2O7Nonlinear optical crystal and its preparation method and purposes
CN107059123A (en) * 2017-01-18 2017-08-18 南开大学 The preparation method and its usage of four metaphosphoric acid dipotassium strontium crystals
CN106868591A (en) * 2017-02-27 2017-06-20 河南理工大学 A kind of preparation of novel light-emitting crystalline material dysprosium phosphate sodium, performance and purposes

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Crystal structure, magnetic and infrared spectroscopy studies of the LiCryFe1-yP2O7 solid solution;Hssain Bih 等;《Journal of Solid State Chemistry》;20090119;第182卷;第821–826页 *
Crystal Structures of Na2ZnP2O7, K2ZnP2O7, and LiKZnP2O7 Phases in the M2O–ZnO–P2O5 Glass-Forming System (M=Li, Na, and K);Yu. F. Shepelev 等;《Glass Physics and Chemistry》;20021231;第28卷(第5期);第317–321页 *
The Structure of Na4P2O7 at 22C;K. Y. LEUNG 等;《Canadian Journal of Chemistry》;19720815;第50卷(第16期);第2519-2526页 *
Vibrational spectra of double diphosphates CsLnP2O7 (Ln＝Gd, Tb, Dy, Ho, Y, Er, Tm, Yb);N. Khay 等;《Journal of Alloys and Compounds》;20011231;第323–324卷;第800–805页 *

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