CN110344119A - Three cesium sulfate calcium non-linear optical crystals and its preparation method and purposes - Google Patents

Three cesium sulfate calcium non-linear optical crystals and its preparation method and purposes Download PDF

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Publication number
CN110344119A
CN110344119A CN201910643025.6A CN201910643025A CN110344119A CN 110344119 A CN110344119 A CN 110344119A CN 201910643025 A CN201910643025 A CN 201910643025A CN 110344119 A CN110344119 A CN 110344119A
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nonlinear optical
crystal
optical crystal
preparation
warming
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沈耀国
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Minjiang University
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Minjiang University
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B9/00—Single-crystal growth from melt solutions using molten solvents
    • C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
    • C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
    • C30B9/12—Salt solvents, e.g. flux growth
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/3551—Crystals

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Inorganic Chemistry (AREA)
  • Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention belongs to nonlinear optical material fields, and in particular to a kind of Cs2Ca2(SO4)3Nonlinear optical crystal and preparation method thereof and its preparing the application in device for non-linear optical.It is with Cs2SO4It is raw material with the sulfate containing Ca, Cs is made through being sintered2Ca2(SO4)3Crystallite；By Cs2Ca2(SO4)3Crystallite and fluxing agent Cs2SO4Block-like Cs is made by spontaneous crystallization in salt mixed melting2Ca2(SO4)3Nonlinear optical crystal.Present invention obtains Cs2Ca2(SO4)3Pure phase and monocrystalline, synthetic method is simple, yield is high；The crystal has shorter ultraviolet cut-on side, moderate frequency-doubling conversion efficiency and good habit, can be used for the device for non-linear optical such as frequency conversion, optical parametric oscillation, Electro-optical Modulation and communication.

Description

Three cesium sulfate calcium non-linear optical crystals and its preparation method and purposes
Technical field
The invention belongs to nonlinear optical material fields, and in particular to a kind of Cs2Ca2(SO4)3Nonlinear optical crystal and Preparation method and its preparing the application in device for non-linear optical.
Background technique
The nonlinear optical effect of crystal refers to: when a branch of laser with certain polarization direction passes through one in certain direction When block nonlinear optical crystal, the frequency of the light beam will change.Crystal with nonlinear optical effect is referred to as non-linear Optical crystal.Using the nonlinear optical effect of crystal, can be made second harmonic generator and upper and lower frequency converter and The device for non-linear optical such as optical parametric oscillator, and all solid state laser of frequency transformation is carried out using nonlinear optical crystal It is a developing direction of the following laser, but its key is to obtain outstanding nonlinear optical crystal.
Currently, being applied to the nonlinear optical crystal of ultraviolet band mainly hasβ-BaB2O4(BBO), LiB3O5(LBO), CsLiB6O10(CLBO) and K2Be2BO3F2(KBBF) etc., but all there is respective shortcoming in them.For example, LBO's is birefringent Rate is all smaller, can not achieve the quadruple output of 1064 nm wavelength lasers；The birefringence of BBO is bigger than normal, is used for 1064 nm There are photorefractive effect when the quadruple output of wavelength laser, its output power and beam quality are limited；And CLBO is easily damp Solution, it is difficult to realize commercial applications；KBBF then due to its serious layer growth habit, causes it to be difficult to obtaincIt is big to thickness Crystal.Therefore, it is still urgent and necessary for exploring the new ultra-violet nonlinear optical crystal of excellent combination property.
Summary of the invention
The purpose of the present invention is to provide a kind of Cs2Ca2(SO4)3Nonlinear optical crystal and the preparation method and application thereof.
To achieve the above object, the present invention adopts the following technical scheme:
The present invention first to be protected is a kind of Cs2Ca2(SO4)3The preparation method of nonlinear optical crystal, wherein using solid Phase reaction method prepares powdered Cs2Ca2(SO4)3Crystallite, and then the block-like Cs of body is prepared by using melt method for growing2Ca2 (SO4)3Nonlinear optical crystal.
Cs is prepared using solid reaction process2Ca2(SO4)3The specific steps of crystallite are as follows: contain Cs2SO4It is pressed with the sulfate containing Ca Stoichiometric ratio according to Cs, Ca be 1:1 after evenly mixing, be warming up to 400 ~ 600 DEG C with 10 ~ 200 DEG C/h of rate, protect Temperature sintering 12 ~ 72 hours, is then down to room temperature, takes out, and grinding uniformly, then is warming up to 600 with 10 ~ 200 DEG C/h of rate ~ It 900 DEG C (calefactive interzone should take out grinding 2 times or more), is sintered 24 ~ 150 hours, obtains Cs2Ca2(SO4)3Crystallite.
Body bulk Cs is prepared using melt method for growing2Ca2(SO4)3The specific steps of nonlinear optical crystal are as follows: to solid phase The Cs of method preparation2Ca2(SO4)3Fluxing agent Cs is added in crystallite2SO4, molar ratio are as follows: Cs2Ca2(SO4)3Crystallite/Cs2SO4=1/(0~ 0.5)；Said mixture is ground meticulously and is placed in crystal growing furnace, being warming up to 700 ~ 1200 DEG C makes it be fused into melt, Room temperature is then rapidly decreased to 600 DEG C with the speed slow cooling of 0.5 ~ 10 DEG C/day again, the block-like Cs of body can be obtained2Mg3 (SO4)4Nonlinear optical crystal.
Wherein the sulfate used containing Ca is CaSO4、CaSO4·0.5H2O、CaSO4·2H2Any one in O.
The present invention second to be protected is the Cs2Ca2(SO4)3Nonlinear optical crystal, the body block being prepared Shape Cs2Ca2(SO4)3Nonlinear optical crystal is free of symmetrical centre, belongs to rhombic systemP213 space groups, structure CaO6It is more Face body and SO4Tetrahedron is total to vertex connection, forms three-dimensional frame structure, and Cs+Ion is filled out in frame hole；Its cell parameter Fora=b=c=10.7040 (4),α=β=γ=90.00 °,V=1226.42(8) Å3,Z=4。
Gained Cs of the invention2Ca2(SO4)3Nonlinear optical crystal is with physical and chemical performance is stable, hardness is moderate, mechanical The advantages that performance is good, not easily broken.
Third of the present invention to be protected is the Cs2Ca2(SO4)3Nonlinear optical crystal is in preparation nonlinear optics device Application in part.The device for non-linear optical includes the nonlinear opticals such as frequency conversion, optical parametric oscillation, Electro-optical Modulation and communication Learn device.
Preferably, the working principle of the device for non-linear optical are as follows: pass through at least a branch of incidence electromagnetic radiation at least One piece of Cs2Ca2(SO4)3After nonlinear optical crystal, the output radiation that at least a branch of frequency is different from incidence electromagnetic radiation is generated.
The beneficial effects of the present invention are: present invention obtains Cs2Ca2(SO4)3Pure phase and monocrystalline, synthetic method letter Single, yield height；The crystal has shorter ultraviolet cut-on side, moderate frequency-doubling conversion efficiency and good habit, can use In device for non-linear optical such as frequency conversion, optical parametric oscillation, Electro-optical Modulation and communications.
Detailed description of the invention
Fig. 1 is Cs prepared by the present invention2Ca2(SO4)3The structural schematic diagram of crystal.
Fig. 2 is Cs prepared by embodiment 12Ca2(SO4)3Polycrystal powder be based on Cs2Ca2(SO4)3The X of crystal structure simulation X ray diffraction compares map.
Fig. 3 is Cs prepared by embodiment 12Ca2(SO4)3The ultraviolet-visible light of polycrystal powder diffuses spectrogram.
Fig. 4 is to utilize prepared Cs2Ca2(SO4)3The work that a kind of typical device for non-linear optical is made in crystal is former Reason figure, wherein 1 is laser, 2 be incoming laser beam, and 3 be the Cs through crystal post-processing and optical manufacturing2Ca2(SO4)3Crystal, 4 It is generated shoot laser beam, 5 be optical filter.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention Technical solution is described further, but the present invention is not limited only to this.
The powdered Cs of embodiment 12Ca2(SO4)3The preparation of compound
It is prepared using solid reaction process, reaction equation is as follows:
Cs2SO4+2CaSO4= Cs2Ca2(SO4)3。
Concrete operation step is: weighing Cs respectively2SO4 1.447 g (0.004 mol)、CaSO4 1.008 g (0.008 Mol), place them into mortar, mix and grind uniformly, be then charged into corundum ceramic crucible, be compacted into, be put into Muffle In furnace, 600 DEG C being warming up to 8 DEG C/h of rate, heat preservation sintering 24 hours, is then down to room temperature, taken out, grinding is uniform, 800 DEG C are warming up to 10 DEG C/h of rate again, is sintered 48 hours, midway takes out grinding 2 times or more to get pure phase Cs2Ca2(SO4)3Compound.
After tested, prepared Cs2Ca2(SO4)3Nonlinear optical crystal is free of symmetrical centre, belongs to rhombic systemP213 Space group；Its cell parameter isa=b=c=10.7040 (4),α=β=γ=90.00 °,V=1226.42(8) Å3,Z=4.Such as Fig. 1 Shown, the structure of the crystal is CaO6Polyhedron and SO4Tetrahedron is total to vertex connection, forms three-dimensional frame structure, and Cs+From Son is filled out in frame hole.
As shown in Fig. 2, prepared compound x-ray diffractogram of powder spectrum with according to its mono-crystalline structures fitting it is resulting Map is consistent.
By resulting Cs2Ca2(SO4)3Nonlinear optical crystal is made diffuse reflectance spectroscopy (such as Fig. 3), the crystal it is ultraviolet It absorbs cut-off and is lower than 200 nm；The crystal is not easily broken, nonhygroscopic.
The powdered Cs of embodiment 22Ca2(SO4)3The preparation of compound
It is prepared using solid reaction process, reaction equation is as follows:
Cs2SO4+2CaSO4·2H2O= Cs2Ca2(SO4)3+4H2O↑
Concrete operation step is: weighing Cs respectively2SO4 1.447 g (0.004 mol)、CaSO4·2H2O 1.377 g (0.008 mol), places them into mortar, mixes and grinds uniformly, is then charged into corundum ceramic crucible, is compacted into, It is put into Muffle furnace, is warming up to 500 DEG C with 40 DEG C/h of rate, heat preservation sintering 24 hours, is then down to room temperature taking-up, Grinding uniformly, then is warming up to 800 DEG C with 55 DEG C/h of rate and is sintered 48 hours, midway take out grinding 2 times or more to get The Cs of pure phase2Ca2(SO4)3Compound crystallite.
3 body bulk Cs of embodiment2Ca2(SO4)3The preparation of crystal
The Cs is prepared using melt method for growing2Ca2(SO4)3Nonlinear optical crystal is by Cs2Ca2(SO4)3Compound is micro- About 3.000 g of crystalline substance are placed in crystal growing furnace, and keeping the temperature 2 hours or more at 1100 DEG C makes it be fused into melt, then with 0.5 DEG C/day slow cooling is then rapidly decreased to room temperature to 600 DEG C, obtains the crystal.
4 body bulk Cs of embodiment2Ca2(SO4)3The preparation of crystal
The Cs is prepared using melt method for growing2Ca2(SO4)3Nonlinear optical crystal is to weigh Cs respectively2Ca2(SO4)3Change Close 3.805 g of object crystallite (0.006 mol) and fluxing agent Cs2SO4They are mixed and are placed on by 0.724 g (0.002 mol) In crystal growing furnace, keeping the temperature 2 hours or more at 1000 DEG C makes it be fused into melt, then extremely with 0.5 DEG C/day slow cooling 600 DEG C, it is then rapidly decreased to room temperature, obtains the crystal.
Crystal of the present invention has frequency-doubled effect.Fig. 4 is to use Cs prepared by the present invention2Ca2(SO4)3Crystal makes non-thread The structural schematic diagram of property optical device.At room temperature, with adjust Q Nd:YAG laser make fundamental frequency light source, by laser 1 issue into Penetrate the near infrared light that laser beam 2(incident wavelength is 1064 nm) inject Cs2Ca2(SO4)3Crystal 3, generated shoot laser beam 4(output wavelength is the green laser of 532 nm) by optical filter 5, thus laser beam required for obtaining, laser intensity about phase When in standard sample KH2PO40.6 times.The nonlinear optics laser can be times frequency generator or upper and lower frequency converter Or optical parametric oscillator etc..
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, is all covered by the present invention.

Claims (5)

1. a kind of Cs2Ca2(SO4)3The preparation method of nonlinear optical crystal, it is characterised in that: the following steps are included:
(1) contain Cs2SO4It is uniformly mixed according to the molar ratio of Cs, Ca for 1:1 with the sulfate containing Ca；
(2) 400 ~ 600 DEG C, heat preservation sintering 12 ~ 72 hours are warming up to 10 ~ 200 DEG C/h of rate；
(3) it then is down to room temperature, taken out, grinding is uniform；
(4) 600 ~ 900 DEG C are warming up to 10 ~ 200 DEG C/h of rate again, are sintered 24 ~ 150 hours, obtain Cs2Ca2(SO4)3It is micro- It is brilliant；
(5) to the Cs of preparation2Ca2(SO4)3Fluxing agent Cs is added in crystallite2SO4, molar ratio are as follows: Cs2Ca2(SO4)3Crystallite/ Cs2SO4=1/(0~0.5)；Said mixture is ground meticulously and is placed in crystal growing furnace, being warming up to 700 ~ 1200 DEG C makes it It is fused into melt, then is then rapidly decreased to room temperature to 600 DEG C with the speed slow cooling of 0.5 ~ 10 DEG C/day, body can be obtained Block-like Cs2Mg3(SO4)4Nonlinear optical crystal.
2. a kind of Cs according to claim 12Ca2(SO4)3The preparation method of nonlinear optical crystal, it is characterised in that: institute Stating the sulfate containing Ca is CaSO4、CaSO4·0.5H2O、CaSO4·2H2Any one in O.
3. a kind of Cs according to claim 12Ca2(SO4)3The preparation method of nonlinear optical crystal, it is characterised in that: institute It states during step (4) is warming up to 600 ~ 900 DEG C and takes out at least twice, ground.
4. a kind of Cs as made from any one of claim 1 ~ 3 the method2Ca2(SO4)3Nonlinear optical crystal, feature exist In: the Cs2Ca2(SO4)3Nonlinear optical crystal is free of symmetrical centre, belongs to rhombic systemP213 space groups, cell parameter Fora=b=c=10.7040 (4),α=β=γ=90.00 °,V=1226.42(8) Å3,Z=4。
5. a kind of Cs as claimed in claim 42Ca2(SO4)3Nonlinear optical crystal is preparing answering in device for non-linear optical With.
CN201910643025.6A 2019-07-17 2019-07-17 Three cesium sulfate calcium non-linear optical crystals and its preparation method and purposes Pending CN110344119A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113122907A (en) * 2021-03-10 2021-07-16 同济大学 Indomethane sulfate second-order nonlinear optical crystal material and preparation and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015165882A1 (en) * 2014-05-01 2015-11-05 Danmarks Tekniske Universitet High-energy pulse compressor using self-defocusing spectral broadening in anomalously dispersive media
CN105350081A (en) * 2015-11-14 2016-02-24 中国科学院新疆理化技术研究所 Preparation method and use of potassium lithium sulfate nonlinear optical crystal
CN109267151A (en) * 2018-11-14 2019-01-25 闽江学院 Three potassium sulfate zinc are preparing the application in device for non-linear optical
CN109295494A (en) * 2018-12-11 2019-02-01 闽江学院 A kind of sulfuric acid difluoro antimony caesium nonlinear optical crystal and its preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015165882A1 (en) * 2014-05-01 2015-11-05 Danmarks Tekniske Universitet High-energy pulse compressor using self-defocusing spectral broadening in anomalously dispersive media
CN105350081A (en) * 2015-11-14 2016-02-24 中国科学院新疆理化技术研究所 Preparation method and use of potassium lithium sulfate nonlinear optical crystal
CN109267151A (en) * 2018-11-14 2019-01-25 闽江学院 Three potassium sulfate zinc are preparing the application in device for non-linear optical
CN109295494A (en) * 2018-12-11 2019-02-01 闽江学院 A kind of sulfuric acid difluoro antimony caesium nonlinear optical crystal and its preparation method and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113122907A (en) * 2021-03-10 2021-07-16 同济大学 Indomethane sulfate second-order nonlinear optical crystal material and preparation and application thereof
CN113122907B (en) * 2021-03-10 2022-04-05 同济大学 Indomethane sulfate second-order nonlinear optical crystal material and preparation and application thereof

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