CN103361726A - Compound sodium-lithium phosphate, sodium-lithium phosphate nonlinear optical crystal, preparation method and application - Google Patents

Compound sodium-lithium phosphate, sodium-lithium phosphate nonlinear optical crystal, preparation method and application Download PDF

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CN103361726A
CN103361726A CN2012100818340A CN201210081834A CN103361726A CN 103361726 A CN103361726 A CN 103361726A CN 2012100818340 A CN2012100818340 A CN 2012100818340A CN 201210081834 A CN201210081834 A CN 201210081834A CN 103361726 A CN103361726 A CN 103361726A
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sodium phosphate
phosphate lithium
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CN103361726B (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 nonlinear optical crystal and preparation method and purposes, which is with composition melting compound, chemical formula LiNa3P2O7, molecular weight 249.85; The chemical formula of sodium phosphate lithium nonlinear optical crystal is LiNa3P2O7, and molecular weight 249.85, space group C2221, cell parameter is a=5.4966 (2), b=9.1365 (4), c=12.2764 (5), Z=4.
Figure DSA00000690386000011
The powder SHG effect of the compound is equivalent to 0.2 times of KDP, transmission region 300nm to 2600nm, synthesizes compound and melt method for crystal growth using solid reaction process. Method of the present invention is easy to operate, at low cost; Prepared crystal does not deliquesce in air, and good mechanical property is not easily broken, and physico-chemical property is stablized, easy processing, 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
The research fields such as the nonlinear optical material crystal is widely used in that laser frequency conversion, four-wave mixing, light beam turn to, image multiplication, optical information processing, optical storage, optical-fibre communications, underwater communication, laser countermeasure (s) and nucleosynthesis.Along with the development of laser technology, the laser frequency doubling crystal that searching can be applied to ultraviolet even deep ultraviolet zone is the focus of scientific circles' research non-linear optic crystal always.
In recent decades, a large amount of borate, phosphoric acid salt are widely studied, and have emerged large quantities of non-linear compound crystalline materials with good frequency-doubled effect, such as BBO, LBO, KBBF, KDP, KTP, DKDP etc.As everyone knows, non-centrosymmetrical structure may present nonlinear optical property.At present, there are a lot of non-centrosymmetrical phosphoric acid salt to be found, for example, K (D xH 1-x) 2PO 4, NH 4H 2PO, K xRb 1-xTiOPO 4, KNd (PO 3) 4Deng.
Research interest to metal phosphate mainly comes from P abundant in the phosphoric acid salt nO mGroup, as: PO 4, P 2O 7, P 3O 10, P 3O 9, P 4O 12And P 6O 18Existing much 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, the further further investigation of phosphate system had important actual application value.
According to current inorganic nonlinear optical crystal Materials situation, the novel inorganic non-linear optic crystal is not only required to have large Clock Multiplier Factor, but also require its over-all properties parameter good, be easy to simultaneously generate high quality and large size body piece crystal, this carries out a large amount of systems and deep research work with regard to needs.
Summary of the invention:
The object of the invention is to be applied to for solution the needs of the nonlinear optical material of all-solid state laser system, and a kind of compound sodium phosphate lithium is provided, and this compound is with the composition melting compound, and chemical formula is LiNa 3P 2O 7, molecular weight is 249.85.
Another purpose of the present invention provides a kind of sodium phosphate lithium non-linear optic crystal, and this crystal is with the composition melting compound, and chemical formula is LiNa 3P 2O 7, molecular weight is 249.85, spacer is C222 1, unit cell parameters is a=5.4966 (2), b=9.1365 (4), c=12.2764 (5), Z=4.
Figure BSA00000690386300021
Figure BSA00000690386300022
Further object of the present invention provides the preparation method who adopts solid reaction process synthetic compound and melt method for growing sodium phosphate lithium non-linear optic crystal.
Another object of the present invention provides 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 the composition melting compound 3P 2O 7, molecular weight is 249.85, adopts the 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, 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 adopts solid reaction process synthetic compound and its crystal of melt method for growing, and concrete operation step is undertaken by following:
A, to contain sodium, contain lithium and P contained compound took by weighing and puts into mortar in 3: 1: 2 in molar ratio, mix and carefully grinding, the corundum crucible of packing into, put into retort furnace, slowly be warming up to 200 ℃, constant temperature 5 hours is cooled to grinding at room temperature even, slowly be warming up to 400 ℃, gas is drained only, take out after cooling crucible, sample is ground evenly, compacting, place again crucible, retort furnace is warming up to 540 ℃, and constant temperature after 72 hours takes out sample, puts into mortar and smashs grinding to pieces and namely get sodium phosphate lithium compound single-phase polycrystalline powder, again this polycrystal powder is carried out X-ray analysis, gained X-ray spectrogram and the finished product monocrystalline last LiNa that pulverizes 3P 2O 7The monocrystalline last X-ray spectrogram of pulverizing is consistent;
B, the polycrystal powder that step a is obtained grind evenly, temperature rise rate with temperature 20-30 ℃/h is heated to 700 ℃ of temperature, constant temperature 20-50 hour, be cooled to again 630 ℃ of temperature and obtain melt, be lowered to fast seed rod in melt, treat that its generation floats crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, then with the speed slow decreasing of temperature 0.5-5 ℃/h to 620 ℃ of temperature, then liquid level is proposed seed rod, speed with temperature 10-50 ℃/h is down to room temperature, obtains sodium phosphate lithium seed crystal;
C, again by step b preparation sodium phosphate lithium melt: the polycrystal powder that step a is obtained grinds evenly, temperature rise rate with temperature 20-30 ℃/h is heated to 700 ℃ of temperature, constant temperature 20-50 hour, be cooled to again 630 ℃ of temperature and obtain melt, the seed crystal that again step b is obtained is fixed on the seed rod, seed crystal under the crystal growing furnace top, elder generation's preheating seed crystal 5-60 minute, then descending makes seed crystal contact or stretch in the melt with bath surface, be down to 625 ℃ of temperature, with the rotating speed rotary seed crystal rod of 20-50rpm, with the speed slow cooling to 620 of temperature 0.5-2 ℃/d ℃, reach crystal growth desired size;
D, after required yardstick is arrived in single crystal growing, crystal is lifted from bath surface, be down to room temperature with the speed of temperature 20-50 ℃/h, then crystal is taken out from burner hearth, can obtain the sodium phosphate crystalline lithium.
The described compound sodium phosphate of step a lithium LiNa 3P 2O 7In contain sodium compound be Na 2CO 3, NaNO 3, Na 2O or NaOH; The compound that contains 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 frequency multiplication producer, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
Compound sodium phosphate lithium of the present invention, this compound is the compound with the composition melting, chemical formula is LiNa 3P 2O 7, molecular weight is 249.85; Sodium phosphate lithium non-linear optic crystal is the compound with the composition melting, and chemical formula is LiNa 3P 2O 7, molecular weight is 249.85, spacer is C222 1, unit cell parameters is a=5.4966 (2), b=9.1365 (4), and c=12.2764 (5), Z=4,
Figure BSA00000690386300031
Figure BSA00000690386300032
Its powder SHG effect is about 0.2 times KDP; The advantages such as transmission region 300nm-2600nm adopts melt method for crystal growth, prepares the sodium phosphate lithium non-linear optic crystal with centimetre-sized size, and 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 adopts general chemical synthesis process can prepare sodium phosphate lithium (LiNa in principle 3P 2O 7) polycrystal raw material, preferred solid reaction process, that is: will contain Na, Li and P mol ratio is that solid state reaction was carried out in heating after 3: 1: 2 raw materials of compound mixed, can obtain chemical formula is LiNa 3P 2O 7Compound.
Preparation 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 among the present invention, contain lithium and P contained compound can adopt commercially available reagent and raw material.
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 making frequency multiplication producer, upper or lower frequency transmodulator and optical parametric oscillator.The described nonlinear device of making of sodium phosphate lithium non-linear optic crystal comprises and will produce the coherent light that a branch of at least frequency is different from incident light through a branch of at least incident fundamental wave.
Described sodium phosphate lithium non-linear optic crystal to the optics working accuracy without particular requirement.
Description of drawings
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 of sodium phosphate crystalline lithium making of the present invention, and wherein: 1 is laser apparatus, and 2 is complete poly-mirror, and 3 for injecting crystal, and 4 is beam splitting prism, and 5 is filter plate.
Embodiment
The present invention is described in detail below in conjunction with drawings and Examples:
Embodiment 1:
Synthetic LiNa 3P 2O 7Compound:
Adopt solid reaction process to carry out sintering under 540 ℃ of high temperature, its chemical equation is: Na 2CO 3+ Li 2CO 3+ NH 4H 2PO 4→ LiNa 3P 2O 7+ H 2O ↑+CO 2↑+NH 3↑
To contain Na, contain Li, contain P-compound and took by weighing in 3: 1: 2 in molar ratio and put into mortar, mix and carefully grind the corundum crucible of packing into, put into retort furnace, slowly be warming up to 200 ℃, constant temperature 5 hours is cooled to grinding at room temperature even, slowly be warming up to 400 ℃, gas is drained only as far as possible, take out after cooling crucible, sample is ground evenly, place again crucible, retort furnace is warming up to 540 ℃, and constant temperature after 72 hours takes out sample, puts into mortar and smashs grinding to pieces and namely get sodium phosphate lithium compound single-phase polycrystalline powder, again this polycrystal powder is carried out X-ray analysis, gained X-ray spectrogram and finished product LiNa 3P 2O 7The monocrystalline last X-ray spectrogram of pulverizing is consistent;
Growing large-size sodium phosphate crystalline lithium in melt:
With synthetic compound sodium phosphate lithium LiNa 3P 2O 7Single-phase polycrystalline powder is packed in the opening platinum crucible of Φ 80mm * 80mm, put into crystal growing furnace, temperature rise rate with 30 ℃/h of temperature is heated to 700 ℃, constant temperature 30 hours, be cooled to again 630 ℃ of temperature, obtain sodium phosphate lithium melt, be lowered to fast seed rod in melt, treat that its generation floats crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, then with the speed slow decreasing of 0.5 ℃/h of temperature to 620 ℃ of temperature, seed rod is proposed liquid level, speed with 10 ℃/h of temperature is down to room temperature, can obtain sodium phosphate lithium seed crystal;
And then preparation sodium phosphate lithium melt: with synthetic compound sodium phosphate lithium LiNa 3P 2O 7Single-phase polycrystalline powder is packed in the opening platinum crucible of Φ 80mm * 80mm, put into crystal growing furnace, temperature rise rate with 30 ℃/h of temperature is heated to 700 ℃, constant temperature 30 hours, be cooled to again 630 ℃ of temperature, obtain sodium phosphate lithium melt, the seed crystal that obtains is fixed on the seed rod, seed crystal under the crystal growing furnace top, elder generation's preheating seed crystal 5 minutes, then descending 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 1 ℃/d of temperature to 620 ℃ of the temperature of crystal desired size;
After required yardstick is arrived in single crystal growing, crystal is lifted from molten surface, be down to room temperature with the speed of 30 ℃/h of temperature, again crystal is taken out from burner hearth, can obtain 20mm * 12mm * 8mm sodium phosphate lithium monocrystalline.
Na in the raw material 2CO 3Replaceable is NaNO 3, Na 2O or NaOH; Li 2CO 3Replaceable is LiF.
Embodiment 2:
Press reaction formula NaNO 3+ Li 2CO 3+ NH 4H 2PO 4→ LiNa 3P 2O 7+ NH 3↑+CO 2↑+NO 2↑+H 2O ↑ synthetic LiNa 3P 2O 7Compound, concrete operation step carries out according to embodiment 1;
With synthetic sodium phosphate lithium LiNa 3P 2O 7The compound single-phase polycrystal powder is packed in the opening platinum crucible of Φ 80mm * 80mm, put into crystal growing furnace, temperature rise rate with 5 ℃/h of temperature heats 700 ℃, constant temperature 35 hours, be cooled to again 630 ℃, obtain sodium phosphate lithium melt, be lowered to fast seed rod in melt, treat that its generation floats crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, then with the speed slow decreasing of 0.5 ℃/h of temperature to 620 ℃ of temperature, seed rod is proposed liquid level, speed with 10 ℃/h of temperature is down to room temperature, can obtain sodium phosphate lithium seed crystal;
And then preparation sodium phosphate lithium melt: with synthetic compound sodium phosphate lithium LiNa 3P 2O 7Single-phase polycrystalline powder is packed in the opening platinum crucible of Φ 80mm * 80mm, put into crystal growing furnace, temperature rise rate with 30 ℃/h of temperature is heated to 700 ℃, constant temperature 30 hours, be cooled to again 630 ℃ of temperature, obtain sodium phosphate lithium melt, the seed crystal that obtains is fixed on the seed rod, seed crystal under the crystal growing furnace top, elder generation's preheating seed crystal 20 minutes, then descending 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 0.5 ℃/d of temperature to 620 ℃ of the temperature of crystal desired size;
After required yardstick is arrived in single crystal growing, crystal is lifted from molten surface, be down to room temperature with the speed of 20 ℃/h of temperature, then crystal is taken out from burner hearth, can obtain 15mm * 10mm * 7mm sodium phosphate lithium monocrystalline.
NaNO in the raw material 3Replaceable be Na 2CO 3, Na 2O or NaOH; Li 2CO 3Replaceable is LiF.
Embodiment 3:
Press reaction formula Na 2O+Li 2CO 3+ NH 4H 2PO 4→ LiNa 3P 2O 7+ CO 2↑+NH 3↑+H 2O ↑ synthetic LiNa 3P 2O 7Compound, concrete operation step carries out according to embodiment 1;
With synthetic compound sodium phosphate lithium LiNa 3P 2O 7Single-phase polycrystalline powder is packed in the opening platinum crucible of Φ 80mm * 80mm, puts into crystal growing furnace, is heated to 700 ℃ with the temperature rise rate of 25 ℃/h of temperature, constant temperature 20 hours, be cooled to again 630 ℃, obtain sodium phosphate lithium melt, be lowered to fast seed rod in melt, treat that its generation floats crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, and with the speed slow decreasing to 620 of 1.5 ℃/h of temperature ℃, seed rod is proposed liquid level, speed with 10 ℃/h of temperature is down to room temperature, can obtain sodium phosphate lithium seed crystal;
And then preparation sodium phosphate lithium melt: with synthetic compound sodium phosphate lithium LiNa 3P 2O 7Single-phase polycrystalline powder is packed in the opening platinum crucible of Φ 80mm * 80mm, put into crystal growing furnace, temperature rise rate with 30 ℃/h of temperature is heated to 700 ℃, constant temperature 30 hours, be cooled to again 630 ℃ of temperature, obtain sodium phosphate lithium melt, the seed crystal that obtains is fixed on the seed rod, seed crystal under the crystal growing furnace top, elder generation's preheating seed crystal 10 minutes, then descending 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 1.5 ℃/d of temperature to 620 ℃ of the temperature of crystal desired size;
After required yardstick is arrived in single crystal growing, crystal is lifted from molten surface, be down to room temperature with the speed of 25 ℃/h of temperature, then crystal is taken out from burner hearth, can obtain 17mm * 14mm * 11mm sodium phosphate lithium monocrystalline.
Na in the raw material 2O is replaceable to be Na 2CO 3, NaOH or NaNO 3Li 2CO 3Replaceable is LiF.
Embodiment 4:
Press reaction formula NaOH+Li 2CO 3+ NH 4H 2PO 4→ LiNa 3P 2O 7+ CO 2↑+H 2O ↑+NH 3↑ synthetic LiNa 3P 2O 7Compound, concrete operation step carries out according to embodiment 1;
With synthetic compound sodium phosphate lithium LiNa 3P 2O 7Single-phase polycrystalline powder in the opening platinum crucible of the Φ 80mm * 80mm that packs into, is put into crystal growing furnace, temperature rise rate with 23 ℃/h of temperature is heated to 700 ℃, and constant temperature 50 hours is cooled to 630 ℃ again, obtain sodium phosphate lithium liquation, be lowered to fast seed rod in melt, treat that its generation floats crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, with the speed slow decreasing to 620 of 0.5 ℃/h of temperature ℃, seed rod is proposed liquid level, be down to room temperature with the speed of 20 ℃/h of temperature, can obtain sodium phosphate lithium seed crystal;
And then preparation sodium phosphate lithium melt: with synthetic compound sodium phosphate lithium LiNa 3P 2O 7Single-phase polycrystalline powder is packed in the opening platinum crucible of Φ 80mm * 80mm, put into crystal growing furnace, temperature rise rate with 30 ℃/h of temperature is heated to 700 ℃, constant temperature 30 hours, be cooled to again 630 ℃ of temperature, obtain sodium phosphate lithium melt, the seed crystal that obtains is fixed on the seed rod, seed crystal under the crystal growing furnace top, elder generation's preheating seed crystal 25 minutes, then descending 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 2 ℃/d of temperature to 620 ℃ of the temperature of crystal desired size;
After required yardstick is arrived in single crystal growing, crystal is lifted from molten surface, be down to room temperature with the speed of 30 ℃/h of temperature, then crystal is taken out from burner hearth, can obtain 12mm * 10mm * 6mm sodium phosphate lithium monocrystalline.
NaOH in the raw material is replaceable to be Na 2CO 3, NaNO 3Or Na 2O; Li 2CO 3Replaceable is LiF.
Embodiment 5:
Press reaction formula Na 2CO 3+ LiF+NH 4H 2PO 4→ L iNa 3P 2O 7+ H 2O ↑+CO 2↑+NH 3↑+HF ↑ synthetic LiNa 3P 2O 7Compound, concrete operation step carries out according to embodiment 1;
With synthetic sodium phosphate lithium LiNa 3P 2O 7The compound single-phase polycrystal powder in the opening platinum crucible of the Φ 80mm * 80mm that packs into, is put into crystal growing furnace, temperature rise rate with 30 ℃/h of temperature is heated to 700 ℃, and constant temperature 40 hours is cooled to 630 ℃ again, obtain sodium phosphate lithium melt, be lowered to fast seed rod in melt, treat that its generation floats crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, with the speed slow cooling to 620 of 5 ℃/h of temperature ℃, seed rod is proposed liquid level, be down to room temperature with the speed of 20 ℃/h of temperature again, can obtain sodium phosphate lithium seed crystal;
And then preparation sodium phosphate lithium melt: with synthetic compound sodium phosphate lithium LiNa 3P 2O 7Single-phase polycrystalline powder is packed in the opening platinum crucible of Φ 80mm * 80mm, put into crystal growing furnace, temperature rise rate with 30 ℃/h of temperature is heated to 700 ℃, constant temperature 30 hours, be cooled to again 630 ℃ of temperature, obtain sodium phosphate lithium melt, the seed crystal that obtains is fixed on the seed rod, seed crystal under the crystal growing furnace top, elder generation's preheating seed crystal 5 minutes, then stretch into as in the melt, with the rotating speed rotary seed crystal rod of 50rpm, with the speed slow cooling of 0.5 ℃/d of temperature to 620 ℃ of the temperature of crystal desired size;
After required yardstick is arrived in single crystal growing, crystal is lifted from molten surface, be down to room temperature with the speed of 35 ℃/h of temperature, crystal is taken out from burner hearth, can obtain 11mm * 9mm * 8mm sodium phosphate lithium monocrystalline.
Na in the raw material 2CO 3Replaceable is NaNO 3, Na 2O or NaOH; LiF is replaceable to be Li 2CO 3
Embodiment 6:
Press reaction formula NaNO 3+ LiF+NH 4H 2PO 4→ LiNa 3P 2O 7+ NH 3↑+NO 2↑+H 2O ↑+HF ↑ synthetic LiNa 3P 2O 7Compound, concrete operation step carries out according to embodiment 1;
With synthetic sodium phosphate lithium LiNa 3P 2O 7The compound single-phase polycrystal powder, pack in the opening platinum crucible of Φ 80mm * 80mm, put into crystal growing furnace, temperature rise rate with 30 ℃/h of temperature is heated to 700 ℃, constant temperature 50 hours, be cooled to again 630 ℃ of temperature, obtain the sodium phosphate melt, be lowered to fast seed rod in melt, treat that its generation floats crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, with the speed slow decreasing of 1.5 ℃/h of temperature to 620 ℃ of temperature, seed rod is proposed liquid level, be down to room temperature with the speed of 35 ℃/h of temperature, can obtain sodium phosphate lithium seed crystal;
And then preparation sodium phosphate lithium melt: with synthetic compound sodium phosphate lithium LiNa 3P 2O 7Single-phase polycrystalline powder is packed in the opening platinum crucible of Φ 80mm * 80mm, put into crystal growing furnace, temperature rise rate with 30 ℃/h of temperature is heated to 700 ℃, constant temperature 30 hours, be cooled to again 630 ℃ of temperature, obtain sodium phosphate lithium melt, the seed crystal that obtains is fixed on the seed rod, seed crystal under the crystal growing furnace top, elder generation's preheating seed crystal 45 minutes, then descend stretch into as in the melt with the rotating speed rotary seed crystal rod of 50rpm, with the speed slow cooling of 2 ℃/d of temperature to 620 ℃ of the temperature of crystal desired size;
After required yardstick is arrived in single crystal growing, crystal is lifted from bath surface, be down to room temperature with the speed of 35 ℃/h of temperature, then crystal is taken out from burner hearth, can obtain 14mm * 11mm * 7mm sodium phosphate lithium monocrystalline.
NaNO in the raw material 3Replaceable is Na 2CO 3, Na 2O or NaOH; LiF is replaceable to be Li 2CO 3
Embodiment 7:
Press reaction formula Na 2O+LiF+NH 4H 2PO 4→ LiNa 3P 2O 7+ NH 3↑+H 2O ↑+HF ↑ synthetic LiNa 3P 2O 7Compound, concrete operation step carries out according to embodiment 1;
With synthetic sodium phosphate lithium LiNa 3P 2O 7The compound single-phase polycrystal powder, pack in the opening platinum crucible of Φ 80mm * 80mm, put into crystal growing furnace, temperature rise rate with 20 ℃/h of temperature is heated to 700 ℃, constant temperature 30 hours, be cooled to again 630 ℃, obtain sodium phosphate lithium melt, be lowered to fast seed rod in melt, treat that its generation floats crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, with the speed slow decreasing of 2 ℃/h of temperature to 620 ℃ of temperature, seed rod is proposed liquid level, be down to room temperature with the speed of 40 ℃/h of temperature, can obtain sodium phosphate lithium seed crystal;
And then preparation sodium phosphate lithium melt: with synthetic compound sodium phosphate lithium LiNa 3P 2O 7Single-phase polycrystalline powder is packed in the opening platinum crucible of Φ 80mm * 80mm, put into crystal growing furnace, temperature rise rate with 30 ℃/h of temperature is heated to 700 ℃, constant temperature 30 hours, be cooled to again 630 ℃ of temperature, obtain sodium phosphate lithium melt, the seed crystal that obtains is fixed on the seed rod, seed crystal under the crystal growing furnace top, elder generation's preheating seed crystal 60 minutes, then descending 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 0.5 ℃/d of temperature to 620 ℃ of the temperature of crystal desired size;
After required yardstick is arrived in single crystal growing, crystal is lifted from bath surface, be down to room temperature with the speed of 40 ℃/h of temperature, then crystal is taken out from burner hearth, can obtain 17mm * 11mm * 10mm sodium phosphate lithium monocrystalline.
Na in the raw material 2O is replaceable to be Na 2CO 3, NaNO 3Or NaOH; LiF is replaceable to be Li 2CO 3
Embodiment 8:
Press reaction formula NaOH+LiF+NH 4H 2PO 4→ LiNa 3P 2O 7+ H 2O ↑+NH 3↑+HF ↑ synthetic LiNa 3P 2O 7Compound, concrete operation step carries out according to embodiment 1;
With synthetic sodium phosphate lithium LiNa 3P 2O 7The compound single-phase polycrystal powder, pack in the opening platinum crucible of Φ 80mm * 80mm, put into crystal growing furnace, temperature rise rate with temperature 50 C/h is heated to 700 ℃, constant temperature 30 hours, be cooled to again 630 ℃ of temperature, obtain sodium phosphate lithium melt, be lowered to fast seed rod in melt, treat that its generation floats crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, with the speed slow decreasing of 1.5 ℃/h of temperature to 620 ℃ of temperature, seed rod is proposed liquid level, be down to room temperature with the speed of 35 ℃/h of temperature, can obtain sodium phosphate lithium seed crystal;
And then preparation sodium phosphate lithium melt: with synthetic compound sodium phosphate lithium LiNa 3P 2O 7Single-phase polycrystalline powder is packed in the opening platinum crucible of Φ 80mm * 80mm, put into crystal growing furnace, temperature rise rate with 30 ℃/h of temperature is heated to 700 ℃, constant temperature 30 hours, be cooled to again 630 ℃ of temperature, obtain sodium phosphate lithium melt, the seed crystal that obtains is fixed on the seed rod, seed crystal under the crystal growing furnace top, elder generation's preheating seed crystal 50 minutes, then descending 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 1.5 ℃/d of temperature to 620 ℃ of the temperature of crystal desired size;
After required yardstick is arrived in single crystal growing, crystal is lifted from bath surface, be down to room temperature with the speed of 30 ℃/h of temperature, then crystal is taken out from burner hearth, can obtain 15mm * 12mm * 9mm sodium phosphate lithium monocrystalline.
NaOH in the raw material is replaceable to be Na 2CO 3, NaNO 3Or Na 2O; LiF is replaceable to be Li 2CO 3
Embodiment 9:
Any crystal with gained among the example 1-8, by being placed in shown in the accompanying drawing on 3 the position, at room temperature, make light source with the 1064nm output of transferring Q Nd:YAG laser apparatus, observe obvious 532nm frequency doubling green light output, output intensity is about 0.2 times of equal conditions KDP; Be that the infrared beam of 1064nm is injected LiNa through convex lens 2 with transferring Q Nd:YAG laser apparatus 1 to send wavelength 3P 2O 7Crystal 3, producing wavelength is the green frequency doubled light of 532nm, and it is the infrared light of 1064nm and the green glow of 532nm that outgoing beam 4 contains wavelength, and filter plate 5 elimination infrared light compositions obtain the green laser that wavelength is 532nm.

Claims (5)

1. a compound sodium phosphate lithium is characterized in that this compound is that chemical formula is: LiNa with the composition melting compound 3P 2O 7, molecular weight is 249.85, adopts the solid reaction process synthetic compound.
2. a compound phosphoric acid salt sodium lithium non-linear optic crystal is characterized in that this crystal is the compound with the composition melting, and chemical formula is LiNa 3P 2O 7, molecular weight is 249.85, spacer is C222 1, unit cell parameters is a=5.4966 (2), b=9.1365 (4), c=12.2764 (5), Z=4.
Figure FSA00000690386200011
Figure FSA00000690386200012
3. the preparation method of sodium phosphate lithium non-linear optic crystal according to claim 2 is characterized in that adopting its crystal of solid reaction process synthetic compound and melt method for growing, and concrete operation step is undertaken by following:
A, to contain sodium, contain lithium and P contained compound took by weighing and puts into mortar in 3: 1: 2 in molar ratio, mix and carefully grinding, the corundum crucible of packing into, put into retort furnace, slowly be warming up to 200 ℃, constant temperature 5 hours is cooled to grinding at room temperature even, slowly be warming up to 400 ℃, gas is drained only, take out after cooling crucible, sample is ground evenly, compacting, place again crucible, retort furnace is warming up to 540 ℃, and constant temperature after 72 hours takes out sample, puts into mortar and smashs grinding to pieces and namely get sodium phosphate lithium compound single-phase polycrystalline powder, again this polycrystal powder is carried out X-ray analysis, gained X-ray spectrogram and the finished product monocrystalline last LiNa that pulverizes 3P 2O 7The monocrystalline last X-ray spectrogram of pulverizing is consistent;
B, the polycrystal powder that step a is obtained grind evenly, temperature rise rate with temperature 20-30 ℃/h is heated to 700 ℃ of temperature, constant temperature 20-50 hour, be cooled to again 630 ℃ of temperature and obtain melt, be lowered to fast seed rod in melt, treat that its generation floats crystalline substance, constant temperature 0.5h floats crystalline substance and does not change, then with the speed slow decreasing of temperature 0.5-5 ℃/h to 620 ℃ of temperature, then liquid level is proposed seed rod, speed with temperature 10-50 ℃/h is down to room temperature, obtains sodium phosphate lithium seed crystal;
C, again by step b preparation sodium phosphate lithium melt: the polycrystal powder that step a is obtained grinds evenly, temperature rise rate with temperature 20-30 ℃/h is heated to 700 ℃ of temperature, constant temperature 20-50 hour, be cooled to again 630 ℃ of temperature and obtain melt, the seed crystal that again step b is obtained is fixed on the seed rod, seed crystal under the crystal growing furnace top, elder generation's preheating seed crystal 5-60 minute, then descending makes seed crystal contact or stretch in the melt with bath surface, be down to 630 ℃ of temperature, with the rotating speed rotary seed crystal rod of 20-50rpm, with the speed slow cooling to 620 of temperature 0.5-2 ℃/d ℃, reach crystal growth desired size;
D, after required yardstick is arrived in single crystal growing, crystal is lifted from bath surface, be down to room temperature with the speed of temperature 20-50 ℃/h, then crystal is taken out from burner hearth, can obtain the sodium phosphate crystalline lithium.
4. method according to claim 3 is characterized in that the described compound sodium phosphate of step a lithium LiNa 3P 2O 7In contain sodium compound be Na 2CO 3, NaNO 3, Na 2O or NaOH; The compound that contains 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 frequency multiplication producer, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
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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
CN106192003A (en) * 2015-05-08 2016-12-07 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
CN106192005A (en) * 2015-05-08 2016-12-07 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
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
CN105839185A (en) * 2016-05-16 2016-08-10 中国科学院福建物质结构研究所 Cs2LiPO4 compound and Cs2LiPO4 nonlinear optical crystal as well as preparation method and application thereof
CN106495121A (en) * 2016-10-14 2017-03-15 中国科学院福建物质结构研究所 CsLiCdP2O7Compound, CsLiCdP2O7Nonlinear 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

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