CN118289808A - Lithium vanadium germanate compound, nonlinear optical crystal thereof, and preparation method and application thereof - Google Patents
Lithium vanadium germanate compound, nonlinear optical crystal thereof, and preparation method and application thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 185
- 150000001875 compounds Chemical class 0.000 title claims abstract description 105
- 230000003287 optical effect Effects 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- DMEJJWCBIYKVSB-UHFFFAOYSA-N lithium vanadium Chemical compound [Li].[V] DMEJJWCBIYKVSB-UHFFFAOYSA-N 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000155 melt Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims description 54
- 238000000227 grinding Methods 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 31
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 150000004820 halides Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 12
- OBTSLRFPKIKXSZ-UHFFFAOYSA-N lithium potassium Chemical compound [Li].[K] OBTSLRFPKIKXSZ-UHFFFAOYSA-N 0.000 claims description 12
- JJFHSTASBVENMB-UHFFFAOYSA-N [Li].[Cs] Chemical compound [Li].[Cs] JJFHSTASBVENMB-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- -1 vanadium lithium rubidium Chemical compound 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 238000007716 flux method Methods 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000004570 mortar (masonry) Substances 0.000 description 14
- 238000011049 filling Methods 0.000 description 10
- DJMZKFUAQIEDKC-UHFFFAOYSA-N lithium rubidium Chemical compound [Li].[Rb] DJMZKFUAQIEDKC-UHFFFAOYSA-N 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 8
- 238000005303 weighing Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 229910003206 NH4VO3 Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910013321 LiB3O5 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Abstract
The invention relates to an XLI 2VGe4O12 (X=K, rb, cs) compound, an XLI 2VGe4O12 (X=K, rb, cs) nonlinear optical crystal, a preparation method and application thereof; the nonlinear optical crystal is of an asymmetric structure, belongs to a monoclinic system and has a space group of C2; the nonlinear optical crystal is prepared by a melt method, a fluxing agent method or a hydrothermal method. The invention also discloses application of the nonlinear optical crystal in a laser nonlinear optical composite functional device and an electro-optical crystal device. The nonlinear optical crystal has high damage threshold, large nonlinear optical effect, high electro-optic coefficient and wide transmission range, and the frequency doubling effect is about 3-8 times of KDP.
Description
Technical Field
The invention relates to the technical field of artificial lenses. More particularly, it relates to potassium lithium vanadate, rubidium lithium vanadate and cesium lithium vanadate compounds, potassium lithium vanadate, rubidium lithium vanadate and cesium lithium vanadate nonlinear optical crystals, and a preparation method and application thereof.
Background
Solid state lasers using laser crystals often produce only a single wavelength of laser light, for example, a common Nd: YAG laser produces only infrared laser light having a laser wavelength of 1064 nm. On this basis, a common means for obtaining lasers in other wavelength ranges is to double or adjust the laser light source of a fixed wavelength by using nonlinear optical effects. Nonlinear optical effects include frequency conversion effects such as frequency multiplication effects, difference frequencies, sum frequencies, and the like. Crystalline materials having the above effects are collectively referred to as nonlinear optical crystalline materials.
With the continuous development of laser technology, lasers with different wavelengths have great demands in the production and living fields of national defense, medical treatment, communication engineering, photoetching technology, laser processing and the like. Therefore, nonlinear optical crystals have important research value as an important means for laser frequency adjustment.
Currently, the nonlinear optical crystal materials used in common use are mainly phosphates for visible and ultraviolet bands, including KDP (KH 2PO4) and KTP (KTiOPO 4), borates for visible, ultraviolet and deep ultraviolet bands, including BBO (β -BaB 2O4)、LBO(LiB3O5) crystals and KBBF (KBe 2BO3F2), and sulfides, selenides and phosphides for mid-far infrared bands, including AGS (AgGaS 2)、AGSe(AgGaSe2) and ZGP (ZnGeP 2), and the like.
For excellent second-order nonlinear optical crystal materials, the spatial group must be non-centrosymmetric, and should have a suitable refractive index to achieve phase matching, and have a sufficiently large frequency multiplication coefficient, a laser damage threshold, and a sufficiently wide light transmission range. However, the crystals known at present have certain disadvantages, which are not satisfactory in practical applications, and therefore the task of exploring new applicable nonlinear optical crystals is urgent.
Disclosure of Invention
The first object of the invention is to provide a class of lithium potassium vanadate, lithium rubidium vanadate and cesium lithium vanadate compounds and a preparation method thereof.
The second object of the invention is to provide a kind of non-linear optical crystal of potassium lithium vanadate, rubidium lithium vanadate and cesium lithium vanadate and a preparation method thereof. The crystal has larger nonlinear optical effect, high electro-optic coefficient and wide transmission range.
The third object of the invention is to provide the application of a type of non-linear optical crystal of potassium lithium vanadate, rubidium lithium vanadate and cesium lithium vanadate.
The invention provides a compound which has a chemical formula of XLI 2VGe4O12, wherein X is K, rb or Cs.
According to the invention, the compound is potassium lithium vanadium germanate and has a chemical formula of KLi 2VGe4O12.
According to the invention, the compound is vanadium lithium rubidium germanate, and the chemical formula is RbLi 2VGe4O12.
According to the invention, the compound is cesium lithium vanadate and has a chemical formula CsLi 2VGe4O12.
The invention also provides a preparation method of the compound, which comprises the following steps:
And mixing and grinding the K-containing compound or the Rb-containing compound or the Cs-containing compound with the Li-containing compound, the V-containing compound and the Ge-containing compound, and calcining to obtain the compound.
According to the invention, the K-containing compound is an oxide of K, a hydroxide of K, a carbonate of K, a halide of K, a nitrate of K or an oxalate of K;
according to the invention, the Rb-containing compound is an oxide of Rb, a hydroxide of Rb, a carbonate of Rb, a halide of Rb, a nitrate of Rb or an oxalate of Rb;
According to the invention, the Cs-containing compound is an oxide of Cs, a hydroxide of Cs, a carbonate of Cs, a halide of Cs, a nitrate of Cs or an oxalate of Cs;
according to the present invention, the Li-containing compound is an oxide of Li, a hydroxide of Li, a carbonate of Li, a halide of Li, a nitrate of Li, or an oxalate of Li;
according to the invention, the V-containing compound is an oxide of V, a hydroxide of V, a halide of V, a nitrate of V, an oxalate of V or ammonium vanadate;
according to the invention, the Ge-containing compound is an oxide of Ge, a hydroxide of Ge, a halide of Ge, a nitrate of Ge or an oxalate of Ge.
According to the invention, the molar ratio of the K-containing compound or Rb-containing compound or Cs-containing compound, li-containing compound, V-containing compound and Ge-containing compound is K or Rb or Cs: li: v: ge=1:2:1:4.
According to the invention, the calcination temperature is 500-900 ℃.
According to the present invention, the preparation method comprises mixing and grinding a K-containing compound or an Rb-containing compound or a Cs-containing compound, a Li-containing compound, a V-containing compound and a Ge-containing compound, presintering, cooling, grinding, and calcining at a high temperature again.
According to the invention, the presintering temperature is, for example, 500-550 ℃, the heating rate is, for example, 10-50 ℃/h, and the time is, for example, 12 hours or more, preferably 24 hours or more.
According to the invention, the calcination temperature is, for example, 700-800 ℃, and the calcination time is, for example, 8 hours or more, preferably 12 hours or more.
The invention also provides a nonlinear optical crystal, which has a chemical formula of XLI 2VGe4O12, wherein X is K, rb or Cs.
According to the invention, the nonlinear crystal is a lithium potassium vanadate nonlinear optical crystal, and the chemical formula is KLi 2VGe4O12; it is of a non-centrosymmetric structure, belongs to a monoclinic system, has a space group of C2 and has a unit cell parameter ofα＝90°，β＝101.2027°，γ＝90°，Z＝2，
According to the invention, the nonlinear crystal is a vanadium lithium rubidium germanate nonlinear optical crystal, and the chemical formula is RbLi 2VGe4O12; it is of a non-centrosymmetric structure, belongs to a monoclinic system, has a space group of C2 and has a unit cell parameter ofα＝90°，β＝100.40°，γ＝90°，Z＝2，
According to the invention, the nonlinear crystal is a cesium lithium vanadate nonlinear optical crystal, and the chemical formula is CsLi 2VGe4O12; it is of a non-centrosymmetric structure, belongs to a monoclinic system, has a space group of C2 and has a unit cell parameter ofα＝90°，β＝100.4013°，γ＝90°，Z＝2，
The invention provides a preparation method of a nonlinear optical crystal, which adopts a melt method to prepare the crystal, and comprises the following steps: mixing and grinding a K-containing compound or an Rb-containing compound or a Cs-containing compound, a Li-containing compound, a V-containing compound and a Ge-containing compound to obtain a raw material; or mixing and grinding the KLi 2VGe4O12、RbLi2VGe4O12 or CsLi 2VGe4O12 polycrystalline powder to obtain a raw material; melting the raw materials, heating to 800-950 ℃, stirring at constant temperature, and cooling to obtain crystals.
The invention also provides a preparation method of the nonlinear optical crystal, which adopts a fluxing agent method to prepare the crystal, and comprises the following steps: grinding and mixing the K-containing compound or the Rb-containing compound or the Cs-containing compound, the Li-containing compound, the V-containing compound, the Ge-containing compound and the fluxing agent uniformly to obtain a raw material; or grinding and uniformly mixing the KLi 2VGe4O12、RbLi2VGe4O12 or CsLi 2VGe4O12 polycrystalline powder and the fluxing agent to obtain a raw material; melting the raw materials, heating to 600-900 ℃, stirring at constant temperature, and cooling to obtain crystals.
The invention also provides a preparation method of the nonlinear optical crystal, which adopts a hydrothermal method to prepare the crystal and comprises the following steps: grinding and mixing the K-containing compound or the Rb-containing compound or the Cs-containing compound, the Li-containing compound, the V-containing compound, the Ge-containing compound and the mineralizer uniformly to obtain a raw material; or grinding and mixing KLi 2VGe4O12、RbLi2VGe4O12 or CsLi 2VGe4O12 polycrystalline powder and mineralizer uniformly to obtain raw materials; mixing the raw materials with water, placing the mixture in a hydrothermal kettle, heating to 100-300 ℃, stirring at constant temperature, and cooling to obtain crystals.
The conditions for growing the crystal by the melt method are as follows: introducing seed crystal at 2-10 deg.c above the saturation point of the melt, cooling at the speed of 0.1-5 deg.c/day, rotating crystal at the speed of 15-50r/min to start crystal growth, raising the crystal to liquid level after the crystal growth is completed, and annealing to room temperature at the cooling rate of 100 deg.c/hr.
The conditions for growing the crystal by the flux method are as follows: introducing seed crystal at 2-10 deg.c above the saturation point of the melt, cooling at the speed of 0.1-5 deg.c/day, rotating crystal at the speed of 15-50r/min to start crystal growth, raising the crystal to liquid level after the crystal growth is completed, and annealing to room temperature at the cooling rate of 100 deg.c/hr.
The conditions for growing the crystal by the hydrothermal method are as follows: introducing seed crystal at 2-10deg.C above saturation point temperature, cooling at a speed of 0.02-5deg.C/day, rotating crystal at a speed of 15-50r/min, starting crystal growth, lifting the crystal from liquid surface after crystal growth is completed, and cooling to room temperature at a cooling rate of no more than 20deg.C/h.
According to the invention, the fluxing agent is one or more of LiF, KF, rbF, csF and MoO 3 in a molar ratio of, for example, liF: KF: rbF: csF: moO 3 =0 to 25:0 to 25:0 to 25:0 to 25:0 to 25. The system grows crystals with high transparency, large crystal size, good optical quality and the like, and is particularly suitable for processing nonlinear optical devices and electro-optical devices.
According to the invention, the mineralizer is, for example, one or more of LiOH, naOH, KOH, rbOH or CsOH; the molar ratio of the mineralizer to the solute is 0-10: 1, the crystal grown by the system has the characteristics of high transparency, good optical quality and the like, and is particularly suitable for processing nonlinear optical devices and electro-optical devices.
The invention also provides the use of the nonlinear optical crystal in nonlinear optical devices, such as laser nonlinear optical composite function devices, electro-optic crystal devices, or lasers.
The invention also provides a nonlinear optical device comprising the nonlinear optical crystal.
According to the present invention, the nonlinear optical device includes, but is not limited to, a laser nonlinear optical compound function device, an electro-optic crystal device, or a laser.
Advantageous effects
The nonlinear optical crystal of potassium lithium vanadate, rubidium lithium vanadate and cesium lithium vanadate provided by the invention has a non-centrosymmetric structure, belongs to a monoclinic system, and can be prepared into the crystal with high quality and large size by adopting a flux method or a hydrothermal method. The nonlinear optical crystal has high damage threshold, large nonlinear optical effect, high electro-optic coefficient and wide transmission range, and the frequency doubling effect is about 3-8 times of KDP. And the crystal has stable physical and chemical properties and is easy to cut, polish, process and store.
The preparation method can prepare large-size transparent nonlinear optical crystals of potassium lithium vanadate, rubidium lithium vanadate and cesium lithium vanadate.
The nonlinear optical crystal of potassium lithium vanadate, rubidium lithium vanadate and cesium lithium vanadate provided by the invention has good application prospects in the aspects of preparing laser nonlinear optical composite functional devices and preparing piezoelectric devices.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
Fig. 1 is a schematic structural diagram of a nonlinear optical crystal of lithium potassium vanadate KLi 2VGe4O12 prepared in example 5 of the present invention.
Fig. 2 is a schematic structural diagram of a nonlinear optical crystal of rubidium lithium vanadate RbLi 2VGe4O12 prepared in example 6 of the present invention.
Fig. 3 is a schematic structural diagram of a nonlinear optical crystal of cesium lithium vanadate CsLi 2VGe4O12 prepared in example 7 of the present invention.
FIG. 4 is a schematic diagram showing the operation of a typical nonlinear optical device made of nonlinear optical crystals in examples 14-16 of the present invention; wherein, the laser comprises a 1-laser, a 2-potassium lithium vanadate or rubidium lithium vanadate or cesium lithium vanadate nonlinear optical crystal and a 3-beam splitter prism.
FIG. 5 is a schematic diagram showing the operation of an exemplary electro-optic device made of a nonlinear optical crystal in accordance with example 17 of the present invention; wherein, the 4-laser, the 5-vanadium lithium potassium germanate or vanadium lithium rubidium germanate or vanadium cesium lithium germanate electro-optic crystal.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments and the accompanying drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
The preparation method in the invention is a conventional method unless otherwise specified.
EXAMPLE 1KLi 2VGe4O12 Compound
The preparation method adopts a solid phase reaction method. And (3) placing K2CO3(1.3820g,0.01mol),Li2CO3(1.4778g,0.02mol),V2O5(1.8188g,0.01mol),GeO2(8.3712g,0.08mol) in a mortar, grinding and mixing uniformly, then placing into a platinum crucible, placing into a muffle furnace, heating to 500 ℃ at a speed of 50 ℃/h for presintering, cooling after preserving heat for 24 hours, taking out a sample after cooling to room temperature, grinding and mixing uniformly again, and placing into the muffle furnace for sintering at 700 ℃ for 12 hours to obtain the polycrystalline KLi 2VGe4O12 compound.
Example 2RbLi 2VGe4O12 Compound
The preparation method adopts a solid phase reaction method. And (3) placing Rb2CO3(2.3094g,0.01mol),Li2CO3(0.4778g,0.02mol),NH4VO3(2.3396g,0.02mol),GeO2(8.3712g,0.08mol) in a mortar, grinding and mixing uniformly, then placing into a platinum crucible, placing into a muffle furnace, heating to 500 ℃ at a speed of 50 ℃/h for presintering, cooling after preserving heat for 24 hours, taking out a sample after cooling to room temperature, grinding and mixing uniformly again, and then placing into the muffle furnace for sintering for 12 hours at 750 ℃ to obtain the polycrystal RbLi 2VGe4O12 compound.
Example 3CsLi 2VGe4O12 Compound
The preparation method adopts a solid phase reaction method. And (3) placing Cs2CO3(3.2582g,0.01mol),Li2O(0.5976g,0.02mol),NH4VO3(2.3396g,0.02mol),GeO2(8.3712g,0.08mol) in a mortar, grinding and mixing uniformly, then placing into a platinum crucible, placing into a muffle furnace, heating to 500 ℃ at a speed of 50 ℃/h for presintering, cooling after preserving heat for 24 hours, taking out a sample after cooling to room temperature, grinding and mixing uniformly again, and placing into the muffle furnace for sintering at 760 ℃ for 12 hours to obtain the polycrystalline CsLi 2VGe4O12 compound.
Example 4
Preparing KLi 2VGe4O12 nonlinear optical crystal by adopting a melt method, comprising the following steps of ：K2CO3(138.2g,1mol),Li2CO3(147.78g,2mol),NH4VO3(233.96g,2mol),GeO2(837.12g,8mol) placing the KLi 2VGe4O12 nonlinear optical crystal in a mortar, grinding and mixing uniformly in the mortar, and then melting and filling the mixture in a crucible with phi 80mm multiplied by 80mm in batches in a muffle furnace; and (3) placing the crucible after material melting into a vertical crystal growth furnace, heating to 925 ℃, stirring at constant temperature for 36h, then cooling to 10 ℃ above a saturation point, introducing seed crystals, cooling at a speed of 0.2 ℃/day, starting crystal growth at a rotation speed of 15r/min, lifting a seed rod after the crystal growth is finished, lifting the crystal off the liquid level, and cooling to room temperature at a speed of 30 ℃/h to obtain the transparent KLi 2VGe4O12 nonlinear optical crystal.
Example 5
The preparation method of the KLi 2VGe4O12 nonlinear optical crystal by adopting a melt method comprises the following steps: 586.475 g of synthesized KLi 2VGe4O12 polycrystalline powder (1 mol) is weighed, ground and mixed uniformly in a mortar, and then melted in batches in a muffle furnace and filled into a crucible with phi 80mm multiplied by 80 mm; and (3) placing the crucible after material melting into a vertical crystal growth furnace, heating to 950 ℃, stirring at constant temperature for 48 hours, then cooling to 5 ℃ above a saturation point, introducing seed crystals, cooling at a speed of 0.5 ℃/day, starting crystal growth at a rotation speed of 10r/min, lifting a seed rod after the crystal growth is finished, lifting the crystal off the liquid level, and cooling to room temperature at a speed of 20 ℃/h to obtain the transparent KLi 2VGe4O12 nonlinear optical crystal.
Example 6
The preparation method of RbLi 2VGe4O12 nonlinear optical crystal by adopting a melt method comprises the following steps: 632.844 g of synthesized RbLi 2VGe4O12 polycrystalline powder (1 mol) is weighed, ground and uniformly mixed in a mortar, and then melted in batches in a muffle furnace and filled in a platinum crucible with phi 90mm multiplied by 90 mm; and (3) placing the crucible after material melting into a vertical crystal growth furnace, heating to 950 ℃, stirring at constant temperature for 72 hours, then cooling to 5 ℃ above a saturation point, introducing seed crystals, cooling at the average speed of 0.4 ℃/day, starting crystal growth at the rotation speed of 10r/min, lifting a seed rod after the crystal growth is finished, lifting the crystal off the liquid level, and cooling to room temperature at the speed of 20 ℃/h to obtain the transparent RbLi 2VGe4O12 nonlinear optical crystal.
Example 7
The preparation method of the CsLi 2VGe4O12 nonlinear optical crystal by adopting the melt method comprises the following steps: 544.225 g of synthesized CsLi 2VGe4O12 polycrystalline powder (0.8 mol) is weighed, ground and mixed uniformly in a mortar, and then melted and filled into a platinum crucible with phi 80mm multiplied by 90mm in batches in a muffle furnace; and (3) placing the crucible after material melting into a vertical crystal growth furnace, heating to 950 ℃, stirring at constant temperature for 48 hours, then cooling to 3 ℃ above a saturation point, introducing seed crystals, cooling at the average speed of 0.4 ℃/day, starting crystal growth at the rotation speed of 10r/min, lifting a seed rod after the crystal growth is finished, lifting the crystal off the liquid level, and cooling to room temperature at the speed of 10 ℃/h to obtain the transparent CsLi 2VGe4O12 nonlinear optical crystal.
Example 8
The method for preparing the KLi 2VGe4O12 nonlinear optical crystal by adopting the fluxing agent method comprises the following steps: taking MoO 3 as a fluxing agent, weighing 586.475 g of synthesized KLi 2VGe4O12 polycrystalline powder (1 mol) and 287.916 g of MoO 3 (2 mol) respectively according to the mol ratio of solute to fluxing agent of 1:2, grinding and uniformly mixing in a mortar, and melting and filling into a crucible with phi 80mm multiplied by 80mm in batches; and (3) placing the crucible after material melting into a vertical crystal growth furnace, heating to 950 ℃, stirring at constant temperature for 48 hours, then cooling to 5 ℃ above a saturation point, introducing seed crystals, cooling at a speed of 0.5 ℃/day, starting crystal growth at a rotation speed of 10r/min, lifting a seed rod after the crystal growth is finished, lifting the crystal off the liquid level, and cooling to room temperature at a speed of 20 ℃/h to obtain the transparent KLi 2VGe4O12 nonlinear optical crystal.
Example 9
The method for preparing RbLi 2VGe4O12 nonlinear optical crystal by adopting a fluxing agent method comprises the following steps: using RbF as a fluxing agent, weighing 632.844 g of synthesized RbLi 2VGe4O12 polycrystalline powder (1 mol) and 313.410 g of RbF (3 mol) respectively according to the mol ratio of solute to fluxing agent of 1:3, grinding and uniformly mixing in a mortar, and melting and filling into a crucible with phi 90mm multiplied by 90mm in batches; and (3) placing the crucible after material melting into a vertical crystal growth furnace, heating to 850 ℃, stirring at constant temperature for 48 hours, then cooling to 5 ℃ above a saturation point, introducing seed crystals, cooling at the average speed of 0.4 ℃/day, starting crystal growth at the rotation speed of 10r/min, lifting a seed rod after the crystal growth is finished, lifting the crystal off the liquid level, and cooling to room temperature at the speed of 20 ℃/h to obtain the transparent RbLi 2VGe4O12 nonlinear optical crystal.
Example 10
The method for preparing the CsLi 2VGe4O12 nonlinear optical crystal by adopting the fluxing agent method comprises the following steps: using LiF-MoO 3 as a fluxing agent, weighing 340.141 g of synthesized CsLi 2VGe4O12 polycrystalline powder (0.5 mol), 25.939 g of LiF (1 mol) and 143.962 g of MoO 3 (1 mol) according to the mol ratio of solute to fluxing agent of 1:2:2, respectively, grinding and uniformly mixing in a mortar, and melting and filling into a crucible with phi 80mm multiplied by 90mm in batches; and (3) placing the crucible after material melting into a vertical crystal growth furnace, heating to 950 ℃, stirring at constant temperature for 48 hours, then cooling to 3 ℃ above a saturation point, introducing seed crystals, cooling at the average speed of 0.4 ℃/day, starting crystal growth at the rotation speed of 10r/min, lifting a seed rod after the crystal growth is finished, lifting the crystal off the liquid level, and cooling to room temperature at the speed of 10 ℃/h to obtain the transparent CsLi 2VGe4O12 nonlinear optical crystal.
Example 11
The preparation method of the KLi 2VGe4O12 nonlinear optical crystal by adopting a hydrothermal method comprises the following steps: taking LiOH as mineralizer, weighing 17.5942 g of synthesized KLi 2VGe4O12 polycrystalline powder (0.03 mol) and 0.3592 g of LiOH (0.015 mol) respectively according to the mol ratio of 1:0.5, grinding and mixing uniformly in a mortar, filling the mixture into a hydrothermal kettle with phi 60mm multiplied by 30mm, and filling the kettle with deionized water by 80%; heating to 180 ℃, keeping the temperature for 48 hours, cooling at the speed of 0.1 ℃/day, lifting the crystal off the liquid surface after the crystal growth is finished, and cooling to room temperature at the speed of 10 ℃/h to obtain the transparent KLi 2VGe4O12 nonlinear optical crystal.
Example 12
The preparation method of RbLi 2VGe4O12 nonlinear optical crystal by adopting a hydrothermal method comprises the following steps: using LiOH as mineralizer, weighing 12.6569 g of synthesized RbLi 2VGe4O12 polycrystalline powder (0.02 mol) and 0.2395 g of LiOH (0.01 mol) respectively according to a molar ratio of 1:0.5, grinding and mixing uniformly in a mortar, filling the mixture into a hydrothermal kettle with phi 60mm multiplied by 30mm, and filling 80% of the kettle with deionized water; heating to 200 ℃, keeping the temperature for 48 hours, cooling at the speed of 0.1 ℃/day, lifting the crystal off the liquid surface after the crystal growth is finished, and cooling to room temperature at the speed of 15 ℃/hour to obtain the transparent RbLi 2VGe4O12 nonlinear optical crystal.
Example 13
The CsLi 2VGe4O12 nonlinear optical crystal is prepared by adopting a hydrothermal method, and comprises the following steps: using LiOH as mineralizer, weighing 6.3284 g of synthesized RbLi 2VGe4O12 polycrystalline powder (0.01 mol) and 0.1198 g of LiOH (0.005 mol) respectively according to the mol ratio of 1:0.5, grinding and mixing uniformly in a mortar, filling into a hydrothermal kettle with phi 30mm multiplied by 30mm, and filling 80% of the kettle with deionized water; heating to 240 ℃, keeping the temperature for 48 hours, cooling at the speed of 0.1 ℃/day, lifting the crystal off the liquid surface after the crystal growth is finished, and cooling to room temperature at the speed of 10 ℃/h to obtain the transparent CsLi 2VGe4O12 nonlinear optical crystal.
Example 14
A nonlinear optical device prepared from KLi 2VGe4O12 crystals:
Cutting into KLi 2VGe4O12 crystal device with cross section size of 3×3mm and light transmission direction length of 10mm according to a certain direction, precisely polishing and coating light transmission surfaces at two ends, and making into optical device according to figure 4, wherein 2 is the above crystal. A1064 nm Q-switched Nd-YAG laser is used as a light source, and green laser with the wavelength of 532nm can be output.
Example 15
A nonlinear optical device prepared from RbLi 2VGe4O12 crystals:
Cutting into RbLi 2VGe4O12 mm crystal device with cross-section size of 5×5mm and light-transmitting direction length of 15mm according to a certain direction, precisely polishing and coating light-transmitting surfaces at two ends, and making into optical device according to figure 4, wherein 2 is the above crystal. A1064 nm Q-switched Nd-YAG laser is used as a light source, and green laser with the wavelength of 532nm can be output.
Example 16
A nonlinear optical device prepared from CsLi 2VGe4O12 crystals:
Cutting into CsLi 2VGe4O12 crystal device with cross-section size of 5×5mm and light-transmitting direction length of 15mm according to a certain direction, precisely polishing and coating light-transmitting surfaces at two ends, and making into optical device according to figure 4, wherein 2 is the above crystal. A1064 nm Q-switched Nd-YAG laser is used as a light source, and green laser with the wavelength of 532nm can be output.
Example 17
An electro-optic crystal device is prepared from KLi 2VGe4O12 crystals:
cutting into a KLi 2VGe4O12 crystal device with a section size of 4X 4mm and a light transmission direction length of 20mm according to a certain direction, precisely polishing light transmission surfaces at two ends, plating gold electrodes on the upper surface and the lower surface, and placing the crystal device at the position of 5 in figure 5 for an electro-optical modulator.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (10)
1. A compound having the chemical formula XLi 2VGe4O12, wherein X is K, rb, or Cs.
2. A process for the preparation of a compound as claimed in claim 1 comprising the steps of: and mixing and grinding the K-containing compound or the Rb-containing compound or the Cs-containing compound with the Li-containing compound, the V-containing compound and the Ge-containing compound, and calcining to obtain the compound.
3. The method for producing a compound according to claim 2, wherein the K-containing compound is an oxide of K, a hydroxide of K, a carbonate of K, a halide of K, a nitrate of K or an oxalate of K;
and/or the Rb-containing compound is an oxide of Rb, a hydroxide of Rb, a carbonate of Rb, a halide of Rb, a nitrate of Rb or an oxalate of Rb;
and/or the Cs-containing compound is an oxide of Cs, a hydroxide of Cs, a carbonate of Cs, a halide of Cs, a nitrate of Cs, or an oxalate of Cs;
And/or the Li-containing compound is an oxide of Li, a hydroxide of Li, a carbonate of Li, a halide of Li, a nitrate of Li, or an oxalate of Li;
and/or the V-containing compound is an oxide of V, a hydroxide of V, a halide of V, a nitrate of V, an oxalate of V or ammonium vanadate;
and/or the Ge-containing compound is an oxide of Ge, a hydroxide of Ge, a halide of Ge, a nitrate of Ge, or an oxalate of Ge;
And/or in the K-containing compound or Rb-containing compound or Cs-containing compound, li-containing compound, V-containing compound and Ge-containing compound, the molar ratio K or Rb or Cs: li: v: ge=1:2:1:4;
preferably, the temperature of the calcination is 500-900 ℃;
Preferably, the preparation method comprises mixing and grinding a K-containing compound or an Rb-containing compound or a Cs-containing compound with a Li-containing compound, a V-containing compound and a Ge-containing compound, presintering, cooling, grinding, and calcining at high temperature again;
The presintering temperature is 500-550 ℃, the heating rate is 10-50 ℃/h, the time is more than 12 hours, and the preferable time is more than 24 hours; the calcination temperature is, for example, 700-800 ℃;
the calcination time is, for example, 8 hours or more, preferably 12 hours or more.
4. A nonlinear optical crystal having the chemical formula XLi 2VGe4O12, wherein X is K, rb, or Cs.
5. The nonlinear optical crystal of claim 4, wherein the nonlinear optical crystal is a potassium lithium vanadate nonlinear optical crystal having a chemical formula of KLi 2VGe4O12; it is of a non-centrosymmetric structure, belongs to a monoclinic system, has a space group of C2 and has a unit cell parameter ofα＝90°，β＝101.2027°，γ＝90°，Z＝2，
And/or the nonlinear optical crystal is a vanadium lithium rubidium germanate nonlinear optical crystal, and the chemical formula is RbLi 2VGe4O12; it is of a non-centrosymmetric structure, belongs to a monoclinic system, has a space group of C2 and has a unit cell parameter ofα＝90°，β＝100.40°，γ＝90°，Z＝2，
And/or the nonlinear optical crystal is a cesium lithium vanadate nonlinear optical crystal, and the chemical formula is CsLi 2VGe4O12; it is of a non-centrosymmetric structure, belongs to a monoclinic system, has a space group of C2 and has a unit cell parameter ofα＝90°，β＝100.4013°，γ＝90°，Z＝2，
6. A method for producing a nonlinear optical crystal as claimed in claims 4 to 5, wherein the crystal is produced by a melt method, comprising the steps of: mixing and grinding a K-containing compound or an Rb-containing compound or a Cs-containing compound, a Li-containing compound, a V-containing compound and a Ge-containing compound to obtain a raw material; or mixing and grinding the KLi 2VGe4O12、RbLi2VGe4O12 or CsLi 2VGe4O12 polycrystalline powder to obtain a raw material; melting the raw materials, heating to 800-950 ℃, stirring at constant temperature, and cooling to obtain crystals;
and/or preparing the crystal by adopting a fluxing agent method, comprising: grinding and mixing the K-containing compound or the Rb-containing compound or the Cs-containing compound, the Li-containing compound, the V-containing compound, the Ge-containing compound and the fluxing agent uniformly to obtain a raw material; or grinding and uniformly mixing the KLi 2VGe4O12、RbLi2VGe4O12 or CsLi 2VGe4O12 polycrystalline powder and the fluxing agent to obtain a raw material; melting the raw materials, heating to 600-900 ℃, stirring at constant temperature, and cooling to obtain crystals;
And/or preparing crystals using a hydrothermal process comprising: grinding and mixing the K-containing compound or the Rb-containing compound or the Cs-containing compound, the Li-containing compound, the V-containing compound, the Ge-containing compound and the mineralizer uniformly to obtain a raw material; or grinding and mixing KLi 2VGe4O12、RbLi2VGe4O12 or CsLi 2VGe4O12 polycrystalline powder and mineralizer uniformly to obtain raw materials; mixing the raw materials with water, placing the mixture in a hydrothermal kettle, heating to 100-300 ℃, stirring at constant temperature, and cooling to obtain crystals.
7. The method for producing a nonlinear optical crystal according to claim 6, wherein the conditions for growing the crystal by the melt method are: introducing seed crystal at 2-10 deg.c above the saturation point of the melt, cooling at the speed of 0.1-5 deg.c/day, rotating crystal at the speed of 15-50r/min to start crystal growth, raising the crystal to liquid level after the crystal growth is completed, and annealing to room temperature at the cooling rate of not greater than 100 deg.c/h;
And/or the conditions for growing crystals by the flux method are as follows: introducing seed crystal at 2-10 deg.c above the saturation point of the melt, cooling at the speed of 0.1-5 deg.c/day, rotating crystal at the speed of 15-50r/min to start crystal growth, raising the crystal to liquid level after the crystal growth is completed, and annealing to room temperature at the cooling rate of not greater than 100 deg.c/h;
And/or the conditions for growing crystals by the hydrothermal method are as follows: introducing seed crystal at 2-10 deg.c over saturation point, cooling at speed of 0.02-5 deg.c/day, rotating crystal at speed of 15-50r/min to start crystal growth, raising the crystal to room temperature at cooling rate of not greater than 20 deg.c/h;
Preferably, the fluxing agent is one or more of LiF, KF, rbF, csF and MoO 3 in a molar ratio such as LiF: KF: rbF: csF: moO 3 =0 to 25:0 to 25:0 to 25:0 to 25:0 to 25;
Preferably, the mineralizer is, for example, one or more of LiOH, naOH, KOH, rbOH or CsOH;
preferably, the molar ratio of the mineralizer to the solute is 0-10: 1.
8. Use of a nonlinear optical crystal as claimed in claims 4-5 in a nonlinear optical device, such as a laser nonlinear optical composite function device, an electro-optical crystal device, or a laser.
9. A nonlinear optical device comprising the nonlinear optical crystal recited in claims 4-5.
10. The nonlinear optical device of claim 9, wherein the nonlinear optical device comprises, but is not limited to, a laser nonlinear optical compound function device, an electro-optic crystal device, or a laser.
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| CN118289808A true CN118289808A (en) | 2024-07-05 |
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