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 PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 204
- SNVQVLIHTDFQDH-UHFFFAOYSA-L [Li+].P(=O)(O)([O-])[O-].[Na+] Chemical compound [Li+].P(=O)(O)([O-])[O-].[Na+] SNVQVLIHTDFQDH-UHFFFAOYSA-L 0.000 title claims abstract description 78
- 230000003287 optical effect Effects 0.000 title claims abstract description 34
- -1 Compound sodium-lithium phosphate Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- 239000000155 melt Substances 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 9
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000011734 sodium Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000012071 phase Substances 0.000 claims description 19
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 238000004061 bleaching Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 238000002083 X-ray spectrum Methods 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 238000010671 solid-state reaction Methods 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 238000002441 X-ray diffraction Methods 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000010431 corundum Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001386 lithium phosphate Inorganic materials 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 235000010344 sodium nitrate Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 32
- 229910052697 platinum Inorganic materials 0.000 description 16
- 239000002994 raw material Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000007844 bleaching agent Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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Abstract
本发明涉及化合物磷酸钠锂和磷酸钠锂非线性光学晶体及制备方法和用途，该化合物为同成份熔融化合物，化学式为LiNa3P2O7，分子量为249.85；磷酸钠锂非线性光学晶体的化学式为LiNa3P2O7，分子量为249.85，空间群为C2221，晶胞参数为a＝5.4966(2)，b＝9.1365(4)，c＝12.2764(5)，Z＝4。
The present invention relates to the compound sodium lithium phosphate and sodium lithium phosphate nonlinear optical crystal and its preparation method and application. The compound is a melting compound with the same composition, the chemical formula is LiNa 3 P 2 O 7 , and the molecular weight is 249.85; the sodium lithium phosphate nonlinear optical crystal The chemical formula is LiNa 3 P 2 O 7 , the molecular weight is 249.85, the space group is C222 1 , the unit cell parameters are a=5.4966(2), b=9.1365(4), c=12.2764(5), Z=4.
Description
技术领域 technical field
本发明涉及一种同成份熔融化合物磷酸钠锂和磷酸钠锂非线性光学晶体及制备方法和用途。The invention relates to a melting compound sodium lithium phosphate and sodium lithium phosphate nonlinear optical crystal with the same composition, a preparation method and application.
背景技术 Background technique
非线性光学材料晶体广泛应用于激光频率转换、四波混频、光束转向、图象放大、光信息处理、光存储、光纤通讯、水下通讯、激光对抗及核聚变等研究领域。随着激光技术的不断发展，寻找能够应用到紫外甚至深紫外区域的激光倍频晶体一直是科学界研究非线性光学晶体的热点。Nonlinear optical material crystals are widely used in research fields such as laser frequency conversion, four-wave mixing, beam steering, image amplification, optical information processing, optical storage, optical fiber communication, underwater communication, laser countermeasures and nuclear fusion. With the continuous development of laser technology, searching for laser frequency-doubling crystals that can be applied to the ultraviolet or even deep ultraviolet region has always been a hot spot in the scientific community to study nonlinear optical crystals.
近几十年来，大量的硼酸盐、磷酸盐被广泛研究，涌现出了一大批具有优良倍频效应的非线性化合物晶体材料，如BBO、LBO、KBBF、KDP、KTP、DKDP等。众所周知，非中心对称的结构可能呈现出非线性光学性质。目前，有很多非中心对称的磷酸盐被发现，例如，K(DxH1-x)2PO4，NH4H2PO，KxRb1-xTiOPO4，KNd(PO3)4等。In recent decades, a large number of borates and phosphates have been widely studied, and a large number of nonlinear compound crystal materials with excellent frequency doubling effects have emerged, such as BBO, LBO, KBBF, KDP, KTP, DKDP, etc. It is well known that non-centrosymmetric structures may exhibit nonlinear optical properties. At present, many non-centrosymmetric phosphates have been found, for example, K(D x H 1-x ) 2 PO 4 , NH 4 H 2 PO, K x Rb 1-x TiOPO 4 , KNd(PO 3 ) 4, etc. .
对金属磷酸盐的研究兴趣主要源于磷酸盐中丰富的PnOm基团，如：PO4、P2O7、P3O10、P3O9、P4O12和P6O18。已有很多关于磷酸盐的报道，如：Li6CuB4O10、Li2Cu5(PO4)4、Ca3(PO4)2、KMgFe(PO4)2、KCuFe(PO4)2等。因此，对磷酸盐体系的进一步深入研究具有重要的实际应用价值。The research interest in metallophosphates is mainly due to the abundant P n O m groups in phosphates, such as: PO 4 , P 2 O 7 , P 3 O 10 , P 3 O 9 , P 4 O 12 and P 6 O 18 . There have been many reports on phosphates, such as: Li 6 CuB 4 O 10 , Li 2 Cu 5 (PO 4 ) 4 , Ca 3 (PO 4 ) 2 , KMgFe(PO 4 ) 2 , KCuFe(PO 4 ) 2 , etc. . Therefore, further in-depth research on the phosphate system has important practical application value.
根据当前无机非线性光学晶体材料发展情况，对新型无机非线性光学晶体不仅要求具有大的倍频系数，而且还要求它的综合性能参数好，同时易于生成优质大尺寸体块晶体，这就需要进行大量系统而深入的研究工作。According to the current development of inorganic nonlinear optical crystal materials, the new inorganic nonlinear optical crystal not only requires a large frequency multiplication coefficient, but also requires its comprehensive performance parameters to be good, and at the same time, it is easy to produce high-quality large-size bulk crystals, which requires Carry out a lot of systematic and in-depth research work.
发明内容：Invention content:
本发明目的在于为解决应用于全固态激光系统的非线性光学材料的需要，提供一种化合物磷酸钠锂，该化合物为同成份熔融化合物，化学式为LiNa3P2O7，分子量为249.85。The object of the present invention is to provide a compound sodium lithium phosphate to meet the needs of nonlinear optical materials used in all-solid-state laser systems. The compound is a molten compound with the same composition, the chemical formula is LiNa 3 P 2 O 7 , and the molecular weight is 249.85.
本发明另一目的是提供一种磷酸钠锂非线性光学晶体，该晶体为同成份熔融化合物，化学式为LiNa3P2O7，分子量为249.85，空间群为C2221，晶胞参数为a＝5.4966(2)，b＝9.1365(4)，c＝12.2764(5)，Z＝4。
本发明再一个目的是提供采用固相反应法合成化合物及熔体法生长磷酸钠锂非线性光学晶体的制备方法。Another object of the present invention is to provide a preparation method for synthesizing compounds by solid state reaction method and growing sodium lithium phosphate nonlinear optical crystal by melt method.
本发明又一个目的是提供一种磷酸钠锂非线性光学晶体的用途。Another object of the present invention is to provide a use of sodium lithium phosphate nonlinear optical crystal.
本发明所述的一种化合物磷酸钠锂，其特征在于该化合物为同成份熔融化合物，化学式为：LiNa3P2O7，分子量为249.85，采用固相反应法合成化合物。A compound of sodium lithium phosphate according to the present invention is characterized in that the compound is a molten compound with the same composition, the chemical formula is: LiNa 3 P 2 O 7 , the molecular weight is 249.85, and the compound is synthesized by a solid-state reaction method.
一种化合物磷酸盐钠锂非线性光学晶体，化学式为LiNa3P2O7，分子量为249.85，空间群为C2221，晶胞参数为a＝5.4966(2)，b＝9.1365(4)，c＝12.2764(5)，Z＝4。 A compound sodium lithium phosphate nonlinear optical crystal, the chemical formula is LiNa 3 P 2 O 7 , the molecular weight is 249.85, the space group is C222 1 , and the unit cell parameters are a=5.4966(2), b=9.1365(4), c =12.2764(5), Z=4.
所述磷酸钠锂非线性光学晶体的制备方法，采用固相反应法合成化合物及熔体法生长其晶体，具体操作步骤按下列进行：The preparation method of the sodium lithium phosphate nonlinear optical crystal adopts the solid phase reaction method to synthesize the compound and the melt method to grow its crystal, and the specific operation steps are as follows:
a、将含钠、含锂和含磷化合物按摩尔比3∶1∶2称取放入研钵中，混合并仔细研磨，装入刚玉坩埚，放入马弗炉中，缓慢升温至200℃，恒温5小时，冷却至室温研磨均匀，缓慢升温至400℃，将气体排干净，待冷却后取出坩埚，将样品研磨均匀、压实，再置于坩埚中，将马弗炉升温至540℃，恒温72小时后将样品取出，放入研钵中捣碎研磨即得磷酸钠锂化合物单相多晶粉末，再对该多晶粉末进行X射线分析，所得X射线谱图与成品单晶研磨成粉末后的LiNa3P2O7单晶研磨成粉末后的X射线谱图是一致的；a. Weigh the sodium-containing, lithium-containing and phosphorus-containing compounds in a molar ratio of 3:1:2 and put them into a mortar, mix and grind carefully, put them into a corundum crucible, put them into a muffle furnace, and slowly heat up to 200°C , keep the temperature for 5 hours, cool to room temperature and grind evenly, slowly heat up to 400°C, drain the gas, take out the crucible after cooling, grind the sample evenly, compact it, put it in the crucible, and heat the muffle furnace to 540°C , take out the sample after 72 hours at constant temperature, put it into a mortar, mash and grind it to get the single-phase polycrystalline powder of sodium lithium phosphate compound, and then carry out X-ray analysis on the polycrystalline powder, the obtained X-ray spectrum is the same as that of the finished single crystal grinding The X-ray spectra of the powdered LiNa 3 P 2 O 7 single crystals ground into powders are consistent;
b、将步骤a得到的多晶粉末研磨均匀，以温度20-30℃/h的升温速率加热至温度700℃，恒温20-50小时，再冷却到温度630℃得到熔体，快速下入籽晶杆到熔体内，待其产生漂晶，恒温0.5h漂晶不化，然后以温度0.5-5℃/h的速率缓慢下降至温度620℃，然后将籽晶杆提出液面，以温度10-50℃/h的速率降至室温，得到磷酸钠锂籽晶；b. Grind the polycrystalline powder obtained in step a evenly, heat up to 700°C at a heating rate of 20-30°C/h, keep the temperature for 20-50 hours, then cool to 630°C to obtain a melt, and quickly insert the seeds Put the crystal rod into the melt, wait for it to produce crystal drift, keep the temperature for 0.5h without bleaching, then slowly drop the temperature at a rate of 0.5-5°C/h to a temperature of 620°C, then lift the seed rod out of the liquid surface, and keep the temperature constant The rate of 10-50°C/h is lowered to room temperature to obtain sodium lithium phosphate seed crystals;
c、再按步骤b配制磷酸钠锂熔体：将步骤a得到的多晶粉末研磨均匀，以温度20-30℃/h的升温速率加热至温度700℃，恒温20-50小时，再冷却到温度630℃得到熔体，再将步骤b得到的籽晶固定于籽晶杆上，从晶体生长炉顶部下籽晶，先预热籽晶5-60分钟，然后下降使籽晶与熔体表面接触或伸入熔体中，降至温度625℃，以20-50rpm的转速旋转籽晶杆，以温度0.5-2℃/d的速率缓慢降温至620℃，达到晶体生长所需尺寸；c. Prepare sodium lithium phosphate melt according to step b: grind the polycrystalline powder obtained in step a evenly, heat to 700°C at a heating rate of 20-30°C/h, keep the temperature for 20-50 hours, and then cool to The temperature is 630°C to obtain the melt, and then the seed crystal obtained in step b is fixed on the seed rod, and the seed crystal is lowered from the top of the crystal growth furnace, and the seed crystal is preheated for 5-60 minutes, and then lowered so that the seed crystal and the melt surface Contact or extend into the melt, lower the temperature to 625°C, rotate the seed rod at a speed of 20-50rpm, and slowly cool down to 620°C at a rate of 0.5-2°C/d to reach the required size for crystal growth;
d、待单晶生长到所需尺度后，将晶体提离熔体表面，以温度20-50℃/h的速率降至室温，然后将晶体从炉膛中取出，即可得到磷酸钠锂晶体。d. After the single crystal grows to the required size, the crystal is lifted from the melt surface, and the temperature is lowered to room temperature at a rate of 20-50°C/h, and then the crystal is taken out from the furnace to obtain sodium lithium phosphate crystal.
步骤a所述化合物磷酸钠锂LiNa3P2O7中含钠的化合物为Na2CO3、NaNO3、Na2O或NaOH；含锂的化合物为Li2CO3或LiF；含磷化合物为NH4H2PO4。The sodium-containing compound in the compound sodium lithium phosphate LiNa 3 P 2 O 7 described in step a is Na 2 CO 3 , NaNO 3 , Na 2 O or NaOH; the lithium-containing compound is Li 2 CO 3 or LiF; the phosphorus-containing compound is NH 4 H 2 PO 4 .
所述磷酸钠锂非线性光学晶体的用途，该晶体用于制备倍频发生器、上频率转换器、下频率转换器或光参量振荡器。The use of the sodium lithium phosphate nonlinear optical crystal, the crystal is used to prepare a frequency doubling generator, an up-frequency converter, a down-frequency converter or an optical parametric oscillator.
本发明所述的化合物磷酸钠锂，该化合物为同成份熔融的化合物，化学式为LiNa3P2O7，分子量为249.85；磷酸钠锂非线性光学晶体为同成份熔融的化合物，化学式为LiNa3P2O7，分子量为249.85，空间群为C2221，晶胞参数为a＝5.4966(2)，b＝9.1365(4)，c＝12.2764(5)，Z＝4，
本发明原则上，采用一般化学合成方法都可以制备磷酸钠锂(LiNa3P2O7)多晶原料，优选固相反应法，即：将含Na、Li和P摩尔比为3∶1∶2的化合物原料混合均匀后，加热进行固相反应，可得到化学式为LiNa3P2O7的化合物。In principle, the present invention can prepare sodium lithium phosphate (LiNa 3 P 2 O 7 ) polycrystalline raw materials by adopting general chemical synthesis methods, preferably the solid phase reaction method, that is: the molar ratio of Na, Li and P is 3:1: After the raw materials of the compound of 2 are mixed evenly, they are heated for solid-state reaction, and the compound with the chemical formula LiNa 3 P 2 O 7 can be obtained.
制备磷酸钠锂(LiNa3P2O7)化合物的化学反应式：The chemical reaction formula for preparing sodium lithium phosphate (LiNa 3 P 2 O 7 ) compound:
(1)Na2CO3+Li2CO3+NH4H2PO4→LiNa3P2O7+H2O↑+CO2↑+NH3↑(1)Na 2 CO 3 +Li 2 CO 3 +NH 4 H 2 PO 4 →LiNa 3 P 2 O 7 +H 2 O↑+CO 2 ↑+NH 3 ↑
(2)NaNO3+Li2CO3+NH4H2PO4→LiNa3P2O7+NH3↑+CO2↑+NO2↑+H2O↑(2)NaNO 3 +Li 2 CO 3 +NH 4 H 2 PO 4 →LiNa 3 P 2 O 7 +NH 3 ↑+CO 2 ↑+NO 2 ↑+H 2 O↑
(3)Na2O+Li2CO3+NH4H2PO4→LiNa3P2O7+CO2↑+NH3↑+H2O↑(3)Na 2 O+Li 2 CO 3 +NH 4 H 2 PO 4 →LiNa 3 P 2 O 7 +CO 2 ↑+NH 3 ↑+H 2 O↑
(4)NaOH+Li2CO3+NH4H2PO4→LiNa3P2O7+CO2↑+H2O↑+NH3↑(4)NaOH+Li 2 CO 3 +NH 4 H 2 PO 4 →LiNa 3 P 2 O 7 +CO 2 ↑+H 2 O↑+NH 3 ↑
(5)Na2CO3+LiF+NH4H2PO4→LiNa3P2O7+H2O↑+CO2↑+NH3↑+HF↑(5)Na 2 CO 3 +LiF+NH 4 H 2 PO 4 →LiNa 3 P 2 O 7 +H 2 O↑+CO 2 ↑+NH 3 ↑+HF↑
(6)NaNO3+LiF+NH4H2PO4→LiNa3P2O7+NH3↑+NO2↑+H2O↑+HF↑(6)NaNO 3 +LiF+NH 4 H 2 PO 4 →LiNa 3 P 2 O 7 +NH 3 ↑+NO 2 ↑+H 2 O↑+HF↑
(7)Na2O+LiF+NH4H2PO4→LiNa3P2O7+NH3↑+H2O↑+HF↑(7)Na 2 O+LiF+NH 4 H 2 PO 4 →LiNa 3 P 2 O 7 +NH 3 ↑+H 2 O↑+HF↑
(8)NaOH+LiF+NH4H2PO4→LiNa3P2O7+H2O↑+NH3↑+HF↑(8)NaOH+LiF+NH 4 H 2 PO 4 →LiNa 3 P 2 O 7 +H 2 O↑+NH 3 ↑+HF↑
本发明中含钠、含锂和含磷化合物可采用市售的试剂及原料。The sodium-containing, lithium-containing and phosphorus-containing compounds in the present invention can use commercially available reagents and raw materials.
所述的化合物磷酸钠锂非线性光学晶体的制备方法，采用熔体法生长晶体。The preparation method of the compound sodium lithium phosphate nonlinear optical crystal adopts the melt method to grow the crystal.
本发明所述的大尺寸的磷酸钠锂(LiNa3P2O7)非线性光学晶体能够制作非线性光学器件，包括制作倍频发生器、上或下频率转换器和光参量振荡器。所述的用磷酸钠锂非线性光学晶体制作的非线性器件包含将透过至少一束入射基波光产生至少一束频率不同于入射光的相干光。The large-sized lithium sodium phosphate (LiNa 3 P 2 O 7 ) nonlinear optical crystal of the present invention can be used to manufacture nonlinear optical devices, including frequency multiplication generators, up or down frequency converters and optical parametric oscillators. The nonlinear device made of sodium lithium phosphate nonlinear optical crystal includes transmitting at least one beam of incident fundamental wave light to generate at least one beam of coherent light with a frequency different from that of the incident light.
所述磷酸钠锂非线性光学晶体对光学加工精度无特殊要求。The sodium lithium phosphate nonlinear optical crystal has no special requirements on optical processing precision.
附图说明 Description of drawings
图1为本发明化合物磷酸钠锂的粉末X-射线衍射图谱。Fig. 1 is the powder X-ray diffraction pattern of compound sodium lithium phosphate of the present invention.
图2为本发明磷酸钠锂晶体的结构图。Fig. 2 is the structural diagram of sodium lithium phosphate crystal of the present invention.
图3为本发明磷酸钠锂晶体制作的非线性光学器件的工作原理图，其中：1为激光器，2为全聚镜，3为射入晶体，4为分光棱镜，5为滤波片。Fig. 3 is the working principle diagram of the nonlinear optical device made of sodium lithium phosphate crystal of the present invention, wherein: 1 is a laser, 2 is an all-condensing mirror, 3 is an incident crystal, 4 is a beam splitting prism, and 5 is a filter.
具体实施方式 Detailed ways
以下结合附图和实施例对本发明进行详细说明：The present invention is described in detail below in conjunction with accompanying drawing and embodiment:
实施例1：Example 1:
合成LiNa3P2O7化合物：Synthesis of LiNa 3 P 2 O 7 compound:
采用固相反应法在高温540℃下进行烧结，其化学方程式是：Na2CO3+Li2CO3+NH4H2PO4→LiNa3P2O7+H2O↑+CO2↑+NH3↑Sintering is carried out at a high temperature of 540°C by a solid-state reaction method, and its chemical equation is: Na 2 CO 3 +Li 2 CO 3 +NH 4 H 2 PO 4 →LiNa 3 P 2 O 7 +H 2 O↑+CO 2 ↑ +NH 3 ↑
将含Na，含Li，含P化合物按摩尔比3∶1∶2称取放入研钵中，混合并仔细研磨，装入刚玉坩埚，放入马弗炉中，缓慢升温至200℃，恒温5小时，冷却至室温研磨均匀，缓慢升温至400℃，尽量将气体排干净，待冷却后取出坩埚，将样品研磨均匀，再置于坩埚中，将马弗炉升温至540℃，恒温72小时后将样品取出，放入研钵中捣碎研磨即得磷酸钠锂化合物单相多晶粉末，再对该多晶粉末进行X射线分析，所得X射线谱图与成品LiNa3P2O7单晶研磨成粉末后X射线谱图是一致的；Weigh the compound containing Na, Li, and P in a molar ratio of 3:1:2, put it into a mortar, mix and grind carefully, put it into a corundum crucible, put it into a muffle furnace, and slowly raise the temperature to 200°C, keep the temperature constant 5 hours, cool to room temperature and grind evenly, slowly heat up to 400°C, drain the gas as much as possible, take out the crucible after cooling, grind the sample evenly, then place it in the crucible, raise the temperature of the muffle furnace to 540°C, and keep the temperature constant for 72 hours Finally, the sample was taken out, put into a mortar, crushed and ground to obtain a single-phase polycrystalline powder of sodium lithium phosphate compound, and then the polycrystalline powder was subjected to X-ray analysis . The X-ray spectrum is consistent after the crystal is ground into powder;
在熔体中生长大尺寸磷酸钠锂晶体：Growth of large-sized lithium sodium phosphate crystals in a melt:
将合成的化合物磷酸钠锂LiNa3P2O7单相多晶粉末装入Φ80mm×80mm的开口铂金坩埚中，放入晶体生长炉中，以温度30℃/h的升温速率加热至700℃，恒温30小时，再冷却到温度630℃，得到磷酸钠锂熔体，快速下入籽晶杆到熔体内，待其产生漂晶，恒温0.5h漂晶不化，然后以温度0.5℃/h的速率缓慢下降至温度620℃，将籽晶杆提出液面，以温度10℃/h的速率降至室温，即可得到磷酸钠锂籽晶；Put the synthesized compound sodium lithium phosphate LiNa 3 P 2 O 7 single-phase polycrystalline powder into a Φ80mm×80mm open platinum crucible, put it into a crystal growth furnace, and heat it to 700°C at a temperature increase rate of 30°C/h. Constant temperature for 30 hours, and then cooled to a temperature of 630°C to obtain a sodium lithium phosphate melt, quickly put the seed rod into the melt, wait for it to produce bleaching crystals, keep the temperature for 0.5h to bleach the crystals, and then set the temperature at 0.5°C/h Slowly lower the rate to a temperature of 620°C, lift the seed rod out of the liquid surface, and lower it to room temperature at a rate of 10°C/h to obtain a sodium lithium phosphate seed;
然后再制备磷酸钠锂熔体：将合成的化合物磷酸钠锂LiNa3P2O7单相多晶粉末装入Φ80mm×80mm的开口铂金坩埚中，放入晶体生长炉中，以温度30℃/h的升温速率加热至700℃，恒温30小时，再冷却到温度630℃，得到磷酸钠锂熔体，将获得的籽晶固定于籽晶杆上，从晶体生长炉顶部下籽晶，先预热籽晶5分钟，然后下降使籽晶与磷酸钠锂熔体表面接触，以20rpm的转速旋转籽晶杆，以温度1℃/d的速率缓慢降温至晶体所需尺寸的温度620℃；Then prepare the sodium lithium phosphate melt: put the synthesized compound sodium lithium phosphate LiNa 3 P 2 O 7 single-phase polycrystalline powder into a Φ80mm×80mm open platinum crucible, put it into a crystal growth furnace, and heat it at a temperature of 30°C/ Heating at a heating rate of h to 700°C, keeping the temperature constant for 30 hours, then cooling to a temperature of 630°C to obtain a sodium lithium phosphate melt, fixing the obtained seed crystal on the seed crystal rod, and lowering the seed crystal from the top of the crystal growth furnace. Heat the seed crystal for 5 minutes, then lower the seed crystal to make contact with the surface of the sodium lithium phosphate melt, rotate the seed crystal rod at a speed of 20 rpm, and slowly cool down to a temperature of 620 °C with the required size of the crystal at a rate of 1 °C/d;
待单晶生长到所需尺度后，将晶体提离熔液表面，以温度30℃/h的速率降至室温，再将晶体从炉膛中取出，即可得到20mm×12mm×8mm磷酸钠锂单晶。After the single crystal grows to the desired size, the crystal is lifted from the surface of the melt, and the temperature is lowered to room temperature at a rate of 30°C/h, and then the crystal is taken out from the furnace to obtain a 20mm×12mm×8mm sodium lithium phosphate single crystal. crystal.
原料中的Na2CO3可替换为NaNO3、Na2O或NaOH；Li2CO3可替换为LiF。Na 2 CO 3 in the raw material can be replaced by NaNO 3 , Na 2 O or NaOH; Li 2 CO 3 can be replaced by LiF.
实施例2：Example 2:
按反应式NaNO3+Li2CO3+NH4H2PO4→LiNa3P2O7+NH3↑+CO2↑+NO2↑+H2O↑合成LiNa3P2O7化合物，具体操作步骤依据实施例1进行；According to the reaction formula NaNO 3 +Li 2 CO 3 +NH 4 H 2 PO 4 →LiNa 3 P 2 O 7 +NH 3 ↑+CO 2 ↑+NO 2 ↑+H 2 O↑ to synthesize the LiNa 3 P 2 O 7 compound, Concrete operation steps are carried out according to embodiment 1;
将合成的磷酸钠锂LiNa3P2O7化合物单相多晶粉末装入Φ80mm×80mm的开口铂金坩埚中，放入晶体生长炉中，以温度5℃/h的升温速率加热700℃，恒温35小时，再冷却到630℃，得到磷酸钠锂熔体，快速下入籽晶杆到熔体内，待其产生漂晶，恒温0.5h漂晶不化，然后以温度0.5℃/h的速率缓慢下降至温度620℃，将籽晶杆提出液面，以温度10℃/h的速率降至室温，即可得到磷酸钠锂籽晶；Put the synthesized sodium lithium phosphate LiNa 3 P 2 O 7 compound single-phase polycrystalline powder into a Φ80mm×80mm open platinum crucible, put it into a crystal growth furnace, and heat it at a temperature of 5°C/h at a rate of 700°C. After 35 hours, cool to 630°C to obtain a sodium-lithium phosphate melt, quickly insert the seed rod into the melt, wait for it to produce bleaching crystals, keep the temperature for 0.5h to bleach the crystals, and then increase the temperature at a rate of 0.5°C/h Slowly lower the temperature to 620°C, lift the seed rod out of the liquid surface, and lower the temperature to room temperature at a rate of 10°C/h to obtain sodium lithium phosphate seed crystals;
然后再制备磷酸钠锂熔体：将合成的化合物磷酸钠锂LiNa3P2O7单相多晶粉末装入Φ80mm×80mm的开口铂金坩埚中，放入晶体生长炉中，以温度30℃/h的升温速率加热至700℃，恒温30小时，再冷却到温度630℃，得到磷酸钠锂熔体，将获得的籽晶固定于籽晶杆上，从晶体生长炉顶部下籽晶，先预热籽晶20分钟，然后下降使籽晶与磷酸钠锂熔体表面接触，以20rpm的转速旋转籽晶杆，以温度0.5℃/d的速率缓慢降温至晶体所需尺寸的温度620℃；Then prepare the sodium lithium phosphate melt: put the synthesized compound sodium lithium phosphate LiNa 3 P 2 O 7 single-phase polycrystalline powder into a Φ80mm×80mm open platinum crucible, put it into a crystal growth furnace, and heat it at a temperature of 30°C/ Heating at a heating rate of h to 700°C, keeping the temperature constant for 30 hours, then cooling to a temperature of 630°C to obtain a sodium lithium phosphate melt, fixing the obtained seed crystal on the seed crystal rod, and lowering the seed crystal from the top of the crystal growth furnace. Heat the seed crystal for 20 minutes, then lower the seed crystal to make contact with the surface of the sodium lithium phosphate melt, rotate the seed crystal rod at a speed of 20 rpm, and slowly cool down to a temperature of 620 °C with the required size of the crystal at a rate of 0.5 °C/d;
待单晶生长到所需尺度后，将晶体提离熔液表面，以温度20℃/h的速率降至室温，然后将晶体从炉膛中取出，即可得到15mm×10mm×7mm磷酸钠锂单晶。After the single crystal grows to the desired size, the crystal is lifted from the surface of the melt, and the temperature is lowered to room temperature at a rate of 20°C/h, and then the crystal is taken out from the furnace to obtain a 15mm×10mm×7mm sodium lithium phosphate single crystal. crystal.
原料中NaNO3的可替换为Na2CO3、Na2O或NaOH；Li2CO3可替换为LiF。NaNO 3 in the raw material can be replaced by Na 2 CO 3 , Na 2 O or NaOH; Li 2 CO 3 can be replaced by LiF.
实施例3：Example 3:
按反应式Na2O+Li2CO3+NH4H2PO4→LiNa3P2O7+CO2↑+NH3↑+H2O↑合成LiNa3P2O7化合物，具体操作步骤依据实施例1进行；Synthesize LiNa 3 P 2 O 7 compound according to the reaction formula Na 2 O+Li 2 CO 3 +NH 4 H 2 PO 4 →LiNa 3 P 2 O 7 +CO 2 ↑+NH 3 ↑+H 2 O ↑ , specific operation steps Carry out according to embodiment 1;
将合成的化合物磷酸钠锂LiNa3P2O7单相多晶粉末装入Φ80mm×80mm的开口铂金坩埚中，放入晶体生长炉中，以温度25℃/h的升温速率加热至700℃，恒温20小时，再冷却到630℃，得到磷酸钠锂熔体，快速下入籽晶杆到熔体内，待其产生漂晶，恒温0.5h漂晶不化，以温度1.5℃/h的速率缓慢下降至620℃，将籽晶杆提出液面，以温度10℃/h的速率降至室温，即可得到磷酸钠锂籽晶；Put the synthesized compound sodium lithium phosphate LiNa 3 P 2 O 7 single-phase polycrystalline powder into a Φ80mm×80mm open platinum crucible, put it into a crystal growth furnace, and heat it to 700°C at a temperature increase rate of 25°C/h. Constant temperature for 20 hours, then cooled to 630°C to obtain sodium lithium phosphate melt, quickly put the seed rod into the melt, wait for it to produce crystal bleaching, keep the temperature for 0.5h and keep the crystal bleaching at a rate of 1.5°C/h Slowly drop to 620°C, lift the seed rod out of the liquid surface, and lower the temperature to room temperature at a rate of 10°C/h to obtain sodium lithium phosphate seed crystals;
然后再制备磷酸钠锂熔体：将合成的化合物磷酸钠锂LiNa3P2O7单相多晶粉末装入Φ80mm×80mm的开口铂金坩埚中，放入晶体生长炉中，以温度30℃/h的升温速率加热至700℃，恒温30小时，再冷却到温度630℃，得到磷酸钠锂熔体，将获得的籽晶固定于籽晶杆上，从晶体生长炉顶部下籽晶，先预热籽晶10分钟，然后下降使籽晶与磷酸钠锂熔体表面接触，以40rpm的转速旋转籽晶杆，以温度1.5℃/d的速率缓慢降温至晶体所需尺寸的温度620℃；Then prepare the sodium lithium phosphate melt: put the synthesized compound sodium lithium phosphate LiNa 3 P 2 O 7 single-phase polycrystalline powder into a Φ80mm×80mm open platinum crucible, put it into a crystal growth furnace, and heat it at a temperature of 30°C/ Heating at a heating rate of h to 700°C, keeping the temperature constant for 30 hours, then cooling to a temperature of 630°C to obtain a sodium lithium phosphate melt, fixing the obtained seed crystal on the seed crystal rod, and lowering the seed crystal from the top of the crystal growth furnace. Heat the seed crystal for 10 minutes, then lower the seed crystal to make contact with the surface of the sodium lithium phosphate melt, rotate the seed crystal rod at a speed of 40 rpm, and slowly cool down to a temperature of 620 °C with the required size of the crystal at a rate of 1.5 °C/d;
待单晶生长到所需尺度后，将晶体提离熔液表面，以温度25℃/h的速率降至室温，然后将晶体从炉膛中取出，即可得到17mm×14mm×11mm磷酸钠锂单晶。After the single crystal grows to the desired size, the crystal is lifted from the surface of the melt, and the temperature is lowered to room temperature at a rate of 25°C/h, and then the crystal is taken out from the furnace to obtain a 17mm×14mm×11mm sodium lithium phosphate single crystal. crystal.
原料中的Na2O可替换为Na2CO3、NaOH或NaNO3；Li2CO3可替换为LiF。Na 2 O in the raw material can be replaced by Na 2 CO 3 , NaOH or NaNO 3 ; Li 2 CO 3 can be replaced by LiF.
实施例4：Example 4:
按反应式 NaOH+Li2CO3+NH4H2PO4→LiNa3P2O7+CO2↑+H2O↑+NH3↑合成LiNa3P2O7化合物，具体操作步骤依据实施例1进行；Synthesize LiNa 3 P 2 O 7 compound according to the reaction formula NaOH+Li 2 CO 3 +NH 4 H 2 PO 4 → LiNa 3 P 2 O 7 +CO 2 ↑+H 2 O↑+NH 3 ↑, the specific operation steps are based on the implementation Example 1 is carried out;
将合成的化合物磷酸钠锂LiNa3P2O7单相多晶粉末，装入Φ80mm×80mm的开口铂金坩埚中，放入晶体生长炉中，以温度23℃/h的升温速率加热至700℃，恒温50小时，再冷却到630℃，得到磷酸钠锂熔液，快速下入籽晶杆到熔体内，待其产生漂晶，恒温0.5h漂晶不化，以温度0.5℃/h的速率缓慢下降至620℃，将籽晶杆提出液面，以温度20℃/h的速率降至室温，即可得到磷酸钠锂籽晶；Put the synthesized compound sodium lithium phosphate LiNa 3 P 2 O 7 single-phase polycrystalline powder into a platinum crucible with an opening of Φ80mm×80mm, put it into a crystal growth furnace, and heat it to 700°C at a heating rate of 23°C/h , constant temperature for 50 hours, and then cooled to 630 ° C to obtain a sodium lithium phosphate melt, quickly put the seed rod into the melt, wait for it to produce crystal drift, and keep the temperature for 0.5 hours. Slowly decrease the rate to 620°C, lift the seed rod out of the liquid surface, and lower it to room temperature at a rate of 20°C/h to obtain sodium lithium phosphate seed crystals;
然后再制备磷酸钠锂熔体：将合成的化合物磷酸钠锂LiNa3P2O7单相多晶粉末装入Φ80mm×80mm的开口铂金坩埚中，放入晶体生长炉中，以温度30℃/h的升温速率加热至700℃，恒温30小时，再冷却到温度630℃，得到磷酸钠锂熔体，将获得的籽晶固定于籽晶杆上，从晶体生长炉顶部下籽晶，先预热籽晶25分钟，然后下降使籽晶与磷酸钠锂熔体表面接触，以30rpm的转速旋转籽晶杆，以温度2℃/d的速率缓慢降温至晶体所需尺寸的温度620℃；Then prepare the sodium lithium phosphate melt: put the synthesized compound sodium lithium phosphate LiNa 3 P 2 O 7 single-phase polycrystalline powder into a Φ80mm×80mm open platinum crucible, put it into a crystal growth furnace, and heat it at a temperature of 30°C/ Heating at a heating rate of h to 700°C, keeping the temperature constant for 30 hours, then cooling to a temperature of 630°C to obtain a sodium lithium phosphate melt, fixing the obtained seed crystal on the seed crystal rod, and lowering the seed crystal from the top of the crystal growth furnace. Heat the seed crystal for 25 minutes, then lower the seed crystal to make contact with the surface of the sodium lithium phosphate melt, rotate the seed crystal rod at a speed of 30 rpm, and slowly cool down at a rate of 2°C/d to a temperature of 620°C for the required size of the crystal;
待单晶生长到所需尺度后，将晶体提离熔液表面，以温度30℃/h的速率降至室温，然后将晶体从炉膛中取出，即可得到12mm×10mm×6mm磷酸钠锂单晶。After the single crystal grows to the required size, the crystal is lifted from the surface of the melt, and the temperature is lowered to room temperature at a rate of 30°C/h, and then the crystal is taken out from the furnace to obtain a 12mm×10mm×6mm sodium lithium phosphate single crystal. crystal.
原料中的NaOH可替换为Na2CO3、NaNO3或Na2O；Li2CO3可替换为LiF。NaOH in the raw material can be replaced by Na 2 CO 3 , NaNO 3 or Na 2 O; Li 2 CO 3 can be replaced by LiF.
实施例5：Example 5:
按反应式 Na2CO3+LiF+NH4H2PO4→L iNa3P2O7+H2O↑+CO2↑+NH3↑+HF↑合成LiNa3P2O7化合物，具体操作步骤依据实施例1进行；According to the reaction formula Na 2 CO 3 +LiF+NH 4 H 2 PO 4 →L iNa 3 P 2 O 7 +H 2 O↑+CO 2 ↑+NH 3 ↑+HF↑ to synthesize LiNa 3 P 2 O 7 compound, specifically Operation steps are carried out according to embodiment 1;
将合成的磷酸钠锂LiNa3P2O7化合物单相多晶粉末，装入Φ80mm×80mm的开口铂金坩埚中，放入晶体生长炉中，以温度30℃/h的升温速率加热至700℃，恒温40小时，再冷却到630℃，得到磷酸钠锂熔体，快速下入籽晶杆到熔体内，待其产生漂晶，恒温0.5h漂晶不化，以温度5℃/h的速率缓慢降温至620℃，将籽晶杆提出液面，再以温度20℃/h的速率降至室温，即可得到磷酸钠锂籽晶；Put the synthesized single-phase polycrystalline powder of sodium lithium phosphate LiNa 3 P 2 O 7 compound into a Φ80mm×80mm open platinum crucible, put it into a crystal growth furnace, and heat it to 700°C at a heating rate of 30°C/h , constant temperature for 40 hours, and then cooled to 630 ° C to obtain a sodium lithium phosphate melt, quickly put the seed rod into the melt, wait for it to produce crystal bleaching, and keep the temperature for 0.5 hours. Slowly lower the temperature to 620°C, lift the seed rod out of the liquid surface, and then lower the temperature to room temperature at a rate of 20°C/h to obtain sodium lithium phosphate seed crystals;
然后再制备磷酸钠锂熔体：将合成的化合物磷酸钠锂LiNa3P2O7单相多晶粉末装入Φ80mm×80mm的开口铂金坩埚中，放入晶体生长炉中，以温度30℃/h的升温速率加热至700℃，恒温30小时，再冷却到温度630℃，得到磷酸钠锂熔体，将获得的籽晶固定于籽晶杆上，从晶体生长炉顶部下籽晶，先预热籽晶5分钟，然后伸入至于熔体中，以50rpm的转速旋转籽晶杆，以温度0.5℃/d的速率缓慢降温至晶体所需尺寸的温度620℃；Then prepare the sodium lithium phosphate melt: put the synthesized compound sodium lithium phosphate LiNa 3 P 2 O 7 single-phase polycrystalline powder into a Φ80mm×80mm open platinum crucible, put it into a crystal growth furnace, and heat it at a temperature of 30°C/ Heating at a heating rate of h to 700°C, keeping the temperature constant for 30 hours, then cooling to a temperature of 630°C to obtain a sodium lithium phosphate melt, fixing the obtained seed crystal on the seed crystal rod, and lowering the seed crystal from the top of the crystal growth furnace. Heat the seed crystal for 5 minutes, then extend it into the melt, rotate the seed crystal rod at a speed of 50 rpm, and slowly cool down at a rate of 0.5°C/d to a temperature of 620°C with the required size of the crystal;
待单晶生长到所需尺度后，将晶体提离熔液表面，以温度35℃/h的速率降至室温，将晶体从炉膛中取出，即可得到11mm×9mm×8mm磷酸钠锂单晶。After the single crystal grows to the required size, the crystal is lifted from the surface of the melt, and the temperature is lowered to room temperature at a rate of 35°C/h, and the crystal is taken out from the furnace to obtain a 11mm×9mm×8mm sodium lithium phosphate single crystal .
原料中的Na2CO3可替换为NaNO3、Na2O或NaOH；LiF可替换为Li2CO3。Na 2 CO 3 in the raw material can be replaced by NaNO 3 , Na 2 O or NaOH; LiF can be replaced by Li 2 CO 3 .
实施例6：Embodiment 6:
按反应式 NaNO3+LiF+NH4H2PO4→LiNa3P2O7+NH3↑+NO2↑+H2O↑+HF↑合成LiNa3P2O7化合物，具体操作步骤依据实施例1进行；According to the reaction formula NaNO 3 +LiF+NH 4 H 2 PO 4 →LiNa 3 P 2 O 7 +NH 3 ↑+NO 2 ↑+H 2 O↑+HF↑ to synthesize LiNa 3 P 2 O 7 compound, the specific operation steps are based on Embodiment 1 carries out;
将合成的磷酸钠锂LiNa3P2O7化合物单相多晶粉末，装入Φ80mm×80mm的开口铂金坩埚中，放入晶体生长炉中，以温度30℃/h的升温速率加热至700℃，恒温50小时，再冷却到温度630℃，得到磷酸钠熔体，快速下入籽晶杆到熔体内，待其产生漂晶，恒温0.5h漂晶不化，以温度1.5℃/h的速率缓慢下降至温度620℃，将籽晶杆提出液面，以温度35℃/h的速率降至室温，即可得到磷酸钠锂籽晶；Put the synthesized single-phase polycrystalline powder of sodium lithium phosphate LiNa 3 P 2 O 7 compound into a Φ80mm×80mm open platinum crucible, put it into a crystal growth furnace, and heat it to 700°C at a heating rate of 30°C/h , constant temperature for 50 hours, and then cooled to a temperature of 630 ° C to obtain a sodium phosphate melt, quickly put the seed rod into the melt, wait for it to produce bleaching, and keep the temperature for 0.5 hours. Slowly lower the rate to a temperature of 620°C, lift the seed rod out of the liquid surface, and lower it to room temperature at a rate of 35°C/h to obtain sodium lithium phosphate seed crystals;
然后再制备磷酸钠锂熔体：将合成的化合物磷酸钠锂LiNa3P2O7单相多晶粉末装入Φ80mm×80mm的开口铂金坩埚中，放入晶体生长炉中，以温度30℃/h的升温速率加热至700℃，恒温30小时，再冷却到温度630℃，得到磷酸钠锂熔体，将获得的籽晶固定于籽晶杆上，从晶体生长炉顶部下籽晶，先预热籽晶45分钟，然后下降伸入至于熔体中以50rpm的转速旋转籽晶杆，以温度2℃/d的速率缓慢降温至晶体所需尺寸的温度620℃；Then prepare the sodium lithium phosphate melt: put the synthesized compound sodium lithium phosphate LiNa 3 P 2 O 7 single-phase polycrystalline powder into a Φ80mm×80mm open platinum crucible, put it into a crystal growth furnace, and heat it at a temperature of 30°C/ Heating at a heating rate of h to 700°C, keeping the temperature constant for 30 hours, then cooling to a temperature of 630°C to obtain a sodium lithium phosphate melt, fixing the obtained seed crystal on the seed crystal rod, and lowering the seed crystal from the top of the crystal growth furnace. Heat the seed crystal for 45 minutes, then descend into the melt and rotate the seed crystal rod at a speed of 50 rpm, and slowly cool down to a temperature of 620°C with the required crystal size at a rate of 2°C/d;
待单晶生长到所需尺度后，将晶体提离熔体表面，以温度35℃/h的速率降至室温，然后将晶体从炉膛中取出，即可得到14mm×11mm×7mm磷酸钠锂单晶。After the single crystal grows to the desired size, the crystal is lifted from the melt surface, and the temperature is lowered to room temperature at a rate of 35°C/h, and then the crystal is taken out from the furnace to obtain a 14mm×11mm×7mm sodium lithium phosphate single crystal. crystal.
原料中的NaNO3可替换为Na2CO3、Na2O或NaOH；LiF可替换为Li2CO3。NaNO 3 in the raw material can be replaced by Na 2 CO 3 , Na 2 O or NaOH; LiF can be replaced by Li 2 CO 3 .
实施例7：Embodiment 7:
按反应式Na2O+LiF+NH4H2PO4→LiNa3P2O7+NH3↑+H2O↑+HF↑合成LiNa3P2O7化合物，具体操作步骤依据实施例1进行；
将合成的磷酸钠锂LiNa3P2O7化合物单相多晶粉末，装入Φ80mm×80mm的开口铂金坩埚中，放入晶体生长炉中，以温度20℃/h的升温速率加热至700℃，恒温30小时，再冷却到630℃，得到磷酸钠锂熔体，快速下入籽晶杆到熔体内，待其产生漂晶，恒温0.5h漂晶不化，以温度2℃/h的速率缓慢下降至温度620℃，将籽晶杆提出液面，以温度40℃/h的速率降至室温，即可得到磷酸钠锂籽晶；Put the synthesized single-phase polycrystalline powder of sodium lithium phosphate LiNa 3 P 2 O 7 compound into a Φ80mm×80mm open platinum crucible, put it into a crystal growth furnace, and heat it to 700°C at a heating rate of 20°C/h , constant temperature for 30 hours, and then cooled to 630 ° C to obtain a sodium lithium phosphate melt, quickly put the seed rod into the melt, wait for it to produce crystal bleaching, and keep the temperature for 0.5 hours. Slowly lower the rate to a temperature of 620°C, lift the seed rod out of the liquid surface, and lower it to room temperature at a rate of 40°C/h to obtain a sodium lithium phosphate seed;
然后再制备磷酸钠锂熔体：将合成的化合物磷酸钠锂LiNa3P2O7单相多晶粉末装入Φ80mm×80mm的开口铂金坩埚中，放入晶体生长炉中，以温度30℃/h的升温速率加热至700℃，恒温30小时，再冷却到温度630℃，得到磷酸钠锂熔体，将获得的籽晶固定于籽晶杆上，从晶体生长炉顶部下籽晶，先预热籽晶60分钟，然后下降使籽晶与磷酸钠锂熔体表面接触，以30rpm的转速旋转籽晶杆，以温度0.5℃/d的速率缓慢降温至晶体所需尺寸的温度620℃；Then prepare the sodium lithium phosphate melt: put the synthesized compound sodium lithium phosphate LiNa 3 P 2 O 7 single-phase polycrystalline powder into a Φ80mm×80mm open platinum crucible, put it into a crystal growth furnace, and heat it at a temperature of 30°C/ Heating at a heating rate of h to 700°C, keeping the temperature constant for 30 hours, then cooling to a temperature of 630°C to obtain a sodium lithium phosphate melt, fixing the obtained seed crystal on the seed crystal rod, and lowering the seed crystal from the top of the crystal growth furnace. Heat the seed crystal for 60 minutes, then lower the seed crystal to contact the surface of the sodium lithium phosphate melt, rotate the seed crystal rod at a speed of 30 rpm, and slowly cool down to a temperature of 620 °C with the required size of the crystal at a rate of 0.5 °C/d;
待单晶生长到所需尺度后，将晶体提离熔体表面，以温度40℃/h的速率降至室温，然后将晶体从炉膛中取出，即可得到17mm×11mm×10mm磷酸钠锂单晶。After the single crystal grows to the desired size, the crystal is lifted from the melt surface, and the temperature is lowered to room temperature at a rate of 40°C/h, and then the crystal is taken out from the furnace to obtain a 17mm×11mm×10mm sodium lithium phosphate single crystal. crystal.
原料中的Na2O可替换为Na2CO3、NaNO3或NaOH；LiF可替换为Li2CO3。Na 2 O in the raw material can be replaced by Na 2 CO 3 , NaNO 3 or NaOH; LiF can be replaced by Li 2 CO 3 .
实施例8：Embodiment 8:
按反应式NaOH+LiF+NH4H2PO4→LiNa3P2O7+H2O↑+NH3↑+HF↑合成LiNa3P2O7化合物，具体操作步骤依据实施例1进行；Synthesize LiNa 3 P 2 O 7 compound according to the reaction formula NaOH+LiF+NH 4 H 2 PO 4 →LiNa 3 P 2 O 7 +H 2 O↑+NH 3 ↑+HF↑, and the specific operation steps are carried out according to Example 1;
将合成的磷酸钠锂LiNa3P2O7化合物单相多晶粉末，装入Φ80mm×80mm的开口铂金坩埚中，放入晶体生长炉中，以温度50℃/h的升温速率加热至700℃，恒温30小时，再冷却至温度630℃，得到磷酸钠锂熔体，快速下入籽晶杆到熔体内，待其产生漂晶，恒温0.5h漂晶不化，以温度1.5℃/h的速率缓慢下降至温度620℃，将籽晶杆提出液面，以温度35℃/h的速率降至室温，即可得到磷酸钠锂籽晶；Put the synthesized sodium lithium phosphate LiNa 3 P 2 O 7 compound single-phase polycrystalline powder into a Φ80mm×80mm open platinum crucible, put it into a crystal growth furnace, and heat it to 700°C at a heating rate of 50°C/h , constant temperature for 30 hours, and then cooled to a temperature of 630°C to obtain a sodium-lithium phosphate melt, quickly put a seed rod into the melt, and wait for it to produce bleaching crystals. Slowly decrease the rate to a temperature of 620°C, lift the seed rod out of the liquid surface, and lower it to room temperature at a rate of 35°C/h to obtain a sodium lithium phosphate seed;
然后再制备磷酸钠锂熔体：将合成的化合物磷酸钠锂LiNa3P2O7单相多晶粉末装入Φ80mm×80mm的开口铂金坩埚中，放入晶体生长炉中，以温度30℃/h的升温速率加热至700℃，恒温30小时，再冷却到温度630℃，得到磷酸钠锂熔体，将获得的籽晶固定于籽晶杆上，从晶体生长炉顶部下籽晶，先预热籽晶50分钟，然后下降使籽晶与磷酸钠锂熔体表面接触，以50rpm的转速旋转籽晶杆，以温度1.5℃/d的速率缓慢降温至晶体所需尺寸的温度620℃；Then prepare the sodium lithium phosphate melt: put the synthesized compound sodium lithium phosphate LiNa 3 P 2 O 7 single-phase polycrystalline powder into a Φ80mm×80mm open platinum crucible, put it into a crystal growth furnace, and heat it at a temperature of 30°C/ Heating at a heating rate of h to 700°C, keeping the temperature constant for 30 hours, then cooling to a temperature of 630°C to obtain a sodium lithium phosphate melt, fixing the obtained seed crystal on the seed crystal rod, and lowering the seed crystal from the top of the crystal growth furnace. Heat the seed crystal for 50 minutes, then lower the seed crystal to contact the surface of the sodium lithium phosphate melt, rotate the seed crystal rod at a speed of 50 rpm, and slowly cool down to a temperature of 620 °C with the required size of the crystal at a rate of 1.5 °C/d;
待单晶生长到所需尺度后，将晶体提离熔体表面，以温度30℃/h的速率降至室温，然后将晶体从炉膛中取出，即可得到15mm×12mm×9mm磷酸钠锂单晶。After the single crystal grows to the desired size, the crystal is lifted from the melt surface, and the temperature is lowered to room temperature at a rate of 30°C/h, and then the crystal is taken out from the furnace to obtain a 15mm×12mm×9mm sodium lithium phosphate single crystal. crystal.
原料中的NaOH可替换为Na2CO3、NaNO3或Na2O；LiF可替换为Li2CO3。NaOH in the raw material can be replaced by Na 2 CO 3 , NaNO 3 or Na 2 O; LiF can be replaced by Li 2 CO 3 .
实施例9：Embodiment 9:
将实例1-8中所得的任意晶体，按附图所示安置在3的位置上，在室温下，用调Q Nd:YAG激光器的1064nm输出作光源，观察到明显的532nm倍频绿光输出，输出强度约为同等条件KDP的0.2倍；用调Q Nd:YAG激光器1发出波长为1064nm的红外光束经全聚透镜2射入LiNa3P2O7晶体3，产生波长为532nm的绿色倍频光，出射光束4含有波长为1064nm的红外光和532nm的绿光，滤波片5滤去红外光成分，得到波长为532nm的绿色激光。Arbitrary crystals obtained in Examples 1-8 are placed at
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