CN101333683B - Novel infrared non-linear crystal CsV2O5 - Google Patents
Novel infrared non-linear crystal CsV2O5 Download PDFInfo
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- CN101333683B CN101333683B CN2007101267791A CN200710126779A CN101333683B CN 101333683 B CN101333683 B CN 101333683B CN 2007101267791 A CN2007101267791 A CN 2007101267791A CN 200710126779 A CN200710126779 A CN 200710126779A CN 101333683 B CN101333683 B CN 101333683B
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- vanadic acid
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- acid caesium
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Abstract
The invention relates to a novel infrared nonlinear crystal cesium vanadate (CVO for short), which belongs to the optics and artificial crystal material fields. The crystal has a molecular formula of CsV2O5, and belongs to an orthorhombic system, the space group is Ima2, and unit cell parameters are: Alpha=Beta=Gamma=90.000. The crystal is yellow and insoluble in water. Analytical reagents of Cs2CO3 and V2O5 are taken as materials in a molar ratio of 1:2 to 1:1.5, and are ground and mixed and then positioned in a platinum crucible which is heated to the temperature of 500 DEG C for obtaining the cesium vanadate. The crystal is congruently melted, and a crystal pulling method or a descent method can be used to grow the crystal. The crystal is used in applications of middle infrared and far infrared regions in the nonlinear optics field.
Description
Technical field:
The present invention relates to optics and artificial crystal material field in the technical field of optoelectronic functional materials, especially relate to a kind of as the mid and far infrared district non-linear optical crystal material in the Laser Modulation operation material.
Background technology:
Nonlinear optics (NLO) functional crystal has very important use in the laser frequency-modulation high-tech sector, be widely used in emerging laser and photoelectron technology field, as technical fields such as opticfiber communication, optical storage, laser processing, laser medicine, laser weapon, laser fusions.At present, existing good NLO crystalline material (potassium primary phosphate KDP, barium metaborate BBO, three lithium tetraborate LBO, potassium titanium oxide phosphate KTP, Lithium niobium trioxide LN, potassium tantalate KT, strontium barium niobate BSN etc.) available application and exploitation from the ultraviolet to the near-infrared band.These crystalline transmission regions can not be as the non-linear optical crystal material of mid and far infrared generally at 2 μ m-5 μ m.Military and medically need seek the non-linear optical crystal material that a class can realize frequency multiplication at the mid and far infrared wave band.The compound of past mid and far infrared NLO crystalline material research concentrates on semiconductor type N-type waferN (Te, CdSe, AgGaS mostly
2, AgGaSe
2, Tl
3AsS
3Deng), be characterized in seeing through wave band and be deep into infrared region, the nonlinear factor height.Shortcoming is that the crystalline size is little, and optical quality is poor, and damage threshold is low, and (uptake factor is at 1-2cm greatly at 3 μ m-5 μ m district uptake factors
-2), thermal conductance is low, can not satisfy the demand of exporting continuously in the interval watt level of 4 μ m-6 μ m.These have all limited this crystal-like actual use.Exploring like this has the compound of anionic group to cause that as the mid and far infrared nonlinear crystalline material people pay attention to widely.These compounds crystalline characteristics are: crystal is grown easily, and optical quality is good, the damage threshold height, but at the mid and far infrared wave band stronger absorption is arranged mostly in them.
Oxygen acid or the salt of secondary group-v element M (M=V, Nb, Ta), because of its anionic group all has the localization of bigger deformability and Cloud Distribution, produce strong macro non-linear effect and electrooptic effect causing strong molecule secondary polarizability under the optical frequency electric field and under the DC electric field.Based on above reason, in niobium (tantalum) hydrochlorate, worked out the big crystalline material of many nonlinear factors, as LiNbO
3, BaTaO
3Deng being good non-linear and electro-optic crystal material all.In the compound of vanadate, also found to have the crystalline material of non-linear optical effect.As LiVO
4The non-linear optical effect of (low temperature phase) just and LiNbO
3Quite.But their infrared absorption can not be as the non-linear optical crystal material of mid and far infrared all under 5 μ m.People such as Su Genbo find K
3V
5O
14The ABSORPTION EDGE red shift of compound is to about the 10 μ m.Transmitance reaches 90%, can be used as the non-linear optical crystal material of mid and far infrared.
Summary of the invention:
Purpose of the present invention just is to disclose a kind of new infrared nonlinear optical crystal vanadic acid caesium.Vanadic acid caesium crystal belongs to rhombic system, has I
Ma2The spacer structure.Belong to the non-centrosymmetry structure.Crystal is congruent melting, and fusing point may be used the melt-growth crystal at 455 ℃.
The vanadic acid caesium can have solid state reaction to obtain, and the synthetic chemical reaction is as follows:
Cs
2CO
3+2V
2O
5→2CsV
2O
5+CO
2↑
Used material purity and producer are as follows:
| The medicine name | Purity | Producer |
| Cs 2CO 3 | 99.9％ | Fengxin, Jiangxi Gan Feng lithium industry company limited |
| V 2O 5 | 99.9％ | Tianjin approaches Dihua worker company limited |
The synthetic condition is as follows:
Use Cs
2CO
3And V
2O
5Reaction at high temperature, raw material is placed in the platinum crucible through ground and mixed, is heated to 500 ℃, and constant temperature 2 ~ 5 hours promptly obtains the vanadic acid caesium.
Growth conditions is as follows:
With adopting crystal pulling method (Czochralski method), the processing parameter of crystal growth is: growth temperature is about 455 ℃, and the crystal rotating speed is 10-15 rev/min, pull rate be the 1.0-1.5 millimeter/hour.Typical process of growth is seen embodiment.
With the vanadic acid caesium [CsV that grows
2O
5] crystal, on single crystal diffractometer, carried out the collection of diffraction data, structural analysis shows that it belongs to rhombic system, spacer is I
Ma2, cell parameter is:
α=β=γ=90.000,
With the vanadic acid caesium [CsV that grows
2O
5] crystal, carrying out Clock Multiplier Factor, infrared spectra, differential thermal and thermogravimetric etc. and analyze test, the result shows: effective Clock Multiplier Factor of vanadic acid caesium is KDP crystal d
3665 times.The crystalline fusing point is not having phase transformation at 455 ℃ below 455 ℃.The seeing through the zone and can reach the mid and far infrared zone of vanadic acid caesium.
Description of drawings:
Fig. 1 is vanadic acid caesium [CsV
2O
5] crystalline structure; Fig. 2 is non-linear optic crystal CsV
2O
5The frequency inverted synoptic diagram that is used for 1.06 mum wavelength laser, wherein 1 is completely reflecting mirror, the 2nd, adjusting Q crystal, the 3rd, polaroid, the 4th, YAG rod, the 5th, output coupling mirror, the 6th, collimating mirror, the 7th, CsV
2O
5Crystal, the 8th, attenuator, the 9th, wavelength is 1.06 laser, the 10th, through CsV
2O
5The laser of the 0.532 μ m that the crystal double frequency conversion produces.
Embodiment:
Realize the specific embodiment of the present invention preferred version 1:
With crystal pulling method (Czochralski method) growth non-linear optic crystal vanadic acid caesium [CsV
2O
5] crystal.
1: the 2 in molar ratio good Cs of accurate weighing
2CO
3And V
2O
5, the mixture mixed grinding is even, puts into platinum crucible, is placed in the retort furnace earlier and calcines, and temperature is 400 ~ 500 ℃, and constant temperature took out after 1 day.Put into the pulling growth stove, be warming up to 500 ℃, reducing to fusing point again, putting into seed crystal, constant temperature half an hour, carrying out the crystalline growth.Growthing process parameter is: growth temperature is about 455 ℃, and the crystal rotating speed is 10-15 rev/min, pull rate be the 1.0-1.5 millimeter/hour.The crystal that grows has optical homogeneity preferably.
Realize the specific embodiment of the present invention preferred version 2:
With reference to Fig. 2, be light source at first with He-Ne laser, adjust each element and make it all on same axis, adjust former and later two chamber sheets of laserresonator, make it parallel; Put into adjusting Q crystal 2 then in light path, open power supply, finely tune the completely reflecting mirror end again, constituting a laserresonator by total reflection 1, adjusting Q crystal 2, polaroid 3, YAG rod 4 and output coupling mirror 5 is the laser oscillator, the laser that is produced is by collimating mirror 6, and it is the infrared laser 9 of 1.06 μ m less than 1 milliradian, wavelength that output promptly obtains the angle of divergence; Again with Cs
3V
5O
14Crystal 7 is placed in the frequency-doubling crystal frame, and the green glow 10 of then exportable 0.53 μ m is observed strong green glow frequency-doubled effect to attenuator 8, and its SHG effect is about 65 times of KDP crystalline.
Claims (4)
1. non-linear optic crystal vanadic acid caesium, it is characterized in that: this crystalline molecular formula is CsV
2O
5, belonging to rhombic system, spacer is I
Ma2, cell parameter is:
α=β=γ=90.000 °,
2. the preparation method of non-linear optic crystal vanadic acid caesium as claimed in claim 1 is characterized in that: use analytical pure Cs
2CO
3And V
2O
5Being raw material, is weighing in 1: 2 in molar ratio, is placed in the platinum crucible through ground and mixed, is heated to 400 ℃～500 ℃, promptly obtains product.
3. the growth method of non-linear optic crystal vanadic acid caesium as claimed in claim 1, it is characterized in that: this crystal by adopting crystal pulling method (Czochralski method) growth, growth conditions: growth temperature is about 455 ℃, the crystal rotating speed is 10-15 rev/min, pull rate be the 1.0-1.5 millimeter/hour.
4. the purposes of non-linear optic crystal vanadic acid caesium as claimed in claim 1 is characterized in that: can change Wavelength of Laser with this crystal, be applied to the non-linear optical field in mid and far infrared district.
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|---|---|---|---|
| CN2007101267791A CN101333683B (en) | 2007-06-29 | 2007-06-29 | Novel infrared non-linear crystal CsV2O5 |
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|---|---|---|---|
| CN2007101267791A CN101333683B (en) | 2007-06-29 | 2007-06-29 | Novel infrared non-linear crystal CsV2O5 |
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|---|---|
| CN101333683A CN101333683A (en) | 2008-12-31 |
| CN101333683B true CN101333683B (en) | 2011-05-04 |
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|---|---|---|---|
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|---|---|---|---|---|
| CN102230221B (en) * | 2011-06-24 | 2015-07-15 | 中国科学院福建物质结构研究所 | Platinum lead iodate serving as second-order non-linear optical crystal |
| CN103396795B (en) * | 2013-07-30 | 2014-12-10 | 苏州大学 | Vanadate fluorescent powder, and preparation method and application thereof |
| CN109853037B (en) * | 2019-03-08 | 2021-02-23 | 武汉科技大学 | Nonlinear optical material cadmium monobromide cesium tetravanadate, and preparation method and application thereof |
| CN111850691B (en) * | 2020-03-12 | 2021-06-04 | 同济大学 | Cesium vanadate infrared frequency doubling crystal material and preparation and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1611641A (en) * | 2003-10-30 | 2005-05-04 | 中国科学院福建物质结构研究所 | Birefraction functional material potassium pentavanadate crystal |
-
2007
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1611641A (en) * | 2003-10-30 | 2005-05-04 | 中国科学院福建物质结构研究所 | Birefraction functional material potassium pentavanadate crystal |
Non-Patent Citations (6)
| Title |
|---|
| A. F. Reid et al.Single Crystal Syntheses by the Electrolyses of Molten Titanates,Molybdates and Vanadates.《JOURNAL OF SOLID STATE CHEMISTRY》.1970,第1卷第310-318页. * |
| A.F.Reidetal.SingleCrystalSynthesesbytheElectrolysesofMoltenTitanates Molybdates and Vanadates.《JOURNAL OF SOLID STATE CHEMISTRY》.1970 |
| JP特开平5-17156A 1993.01.26 |
| Roser Valenti et al.Electronic and magnetic structure of CsV2O5.《PHYSICAL REVIEW B》.2002,第65卷第1-6页. * |
| W. G. Mumme et al.The Crystal Structure of Reduced Cesium Vanadate, CsV2O5.《JOURNAL OF SOLID STATE CHEMISTRY》.1971,第3卷第319-322页. * |
| W.G.Mummeetal.TheCrystalStructureofReducedCesiumVanadate CsV2O5.《JOURNAL OF SOLID STATE CHEMISTRY》.1971 |
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|---|---|
| CN101333683A (en) | 2008-12-31 |
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