CN109137073B - Lithium cesium yttrium phosphate nonlinear optical crystal and preparation method and application thereof - Google Patents

Lithium cesium yttrium phosphate nonlinear optical crystal and preparation method and application thereof Download PDF

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CN109137073B
CN109137073B CN201811102265.7A CN201811102265A CN109137073B CN 109137073 B CN109137073 B CN 109137073B CN 201811102265 A CN201811102265 A CN 201811102265A CN 109137073 B CN109137073 B CN 109137073B
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沈耀国
李玉良
贾俊荣
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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
    • C30B29/14—Phosphates
    • 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
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • 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

Abstract

The invention discloses LiCs2Y2(PO4)3Nonlinear optical crystal and preparation method and application thereof. The LiCs is prepared by sintering Li-containing compound, Cs-containing compound, Y-containing compound and P-containing compound as raw materials2Y2(PO4)3Powdering and then subjecting the resulting LiCs to2Y2(PO4)3Mixing and melting the powder and a fluxing agent to obtain the LiCs2Y2(PO4)3A nonlinear optical crystal. The crystal transparent inclusion-free body prepared by the invention has the advantages of higher growth speed, low cost and the like, has the advantages of shorter ultraviolet absorption cut-off edge, larger nonlinear optical effect, stable physical and chemical properties, good mechanical properties, easy processing and the like, and can be used for manufacturing nonlinear optical devices such as laser blinding weapons, optical disc recording, laser projection televisions, optical computing, optical fiber communication and the like.

Description

Lithium cesium yttrium phosphate nonlinear optical crystal and preparation method and application thereof
Technical Field
The invention relates to LiCs2Y2(PO4)3Nonlinear optical crystal, preparation method thereof and application thereof in preparing nonlinear optical devices.
Background
The nonlinear optical effect of the crystal refers to: when a laser beam with a certain polarization direction passes through a nonlinear optical crystal in a certain direction, the frequency of the beam changes. Crystals with nonlinear optical effects are referred to as nonlinear optical crystals. The nonlinear optical effect of the crystal can be used to make nonlinear optical devices such as second harmonic generators, up and down frequency converters, optical parametric oscillators, etc., and the all-solid-state laser using the nonlinear optical crystal for frequency conversion is also a development direction of future lasers, but the key point is to obtain an excellent nonlinear optical crystal.
At present, the nonlinear optical crystal applied to the ultraviolet band is mainly providedβ-BaB2O4（BBO）、LiB3O5（LBO）、CsLiB6O10(CLBO) and K2Be2BO3F2(KBBF) and the like, but they all have their own disadvantages. For example, the birefringence of LBO is relatively small, and the quadruple frequency output of 1064 nm wavelength laser cannot be realized; the BBO has larger birefringence, and has a photorefractive effect when being used for quadruple frequency output of laser with 1064 nm wavelength, so that the output power and the beam quality are limited; CLBO is extremely easy to deliquesce and difficult to realize commercial application; KBBF is difficult to obtain due to its severe lamellar growth habitcTowards the crystals with large thickness. Therefore, the search for novel ultraviolet nonlinear optical crystals with excellent combination properties is still urgent and necessary.
Disclosure of Invention
The invention aims to provide LiCs2Y2(PO4)3Nonlinear optical crystal and preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first protection of the invention is LiCs2Y2(PO4)3Nonlinear optical crystal, the LiCs2Y2(PO4)3The nonlinear optical crystal does not contain a symmetric center and belongs to a cubic crystal systemP2 13 space group with structure of YO6Octahedron and PO4Tetrahedra connected together at vertices to form a three-dimensional framework, and Li+Ions and Cs+The ions are filled in the holes of the frame; having a cell parameter ofa=b=c=10.5945(5)
Figure 100002_DEST_PATH_IMAGE002
，α=β=γ=90.00，V=1189.16(10)
Figure 100002_DEST_PATH_IMAGE004
，Z=4。
The second protection of the invention is that the LiCs2Y2(PO4)3The preparation method of the nonlinear optical crystal adopts a solid-phase reaction method to prepareLiCs2Y2(PO4)3Powder, and then growing by a melt method to prepare the LiCs2Y2(PO4)3A nonlinear optical crystal; the method specifically comprises the following steps:
1) uniformly mixing a Li-containing compound, a Cs-containing compound, a Y-containing compound and a P-containing compound according to the stoichiometric ratio of Li, Cs, Y and P of 1:2:2:3, heating to 400-500 ℃ at the speed of 10-200 ℃/h, carrying out heat preservation sintering for 12-72 hours, cooling to room temperature, taking out, grinding uniformly, heating to 500-1100 ℃ at the speed of 10-200 ℃/h, and sintering for 24-72 hours to obtain pure-phase LiCs2Y2(PO4)3Powder;
2) mixing flux and LiCs2Y2(PO4)3Mixing the powder, placing the mixture in a crystal growth furnace, heating to 700-1200 ℃ to melt the mixture into a melt, measuring the saturation temperature of the melt, cooling the melt to 5-15 ℃ below the saturation temperature, slowly cooling to 600 ℃ at the speed of 0.5-10 ℃/day, and then rapidly cooling to room temperature to obtain LiCs2Y2(PO4)3A nonlinear optical crystal.
The Li-containing compound in the step 1) is Li2CO3Or LiOH. H2O; the Cs-containing compound is Cs2CO3Or CsNO3(ii) a The compound containing Y is Y2O3(ii) a The P-containing compound is NH4H2PO4Or (NH)4)2HPO4。
The reaction process is as follows: 0.5Li2CO3+Cs2CO3+Y2O3+3NH4H2PO4=LiCs2Y2(PO4)3+1.5CO2↑+4.5H2O↑+3NH3×) ×; or LiOH. H2O+2CsNO3+Y2O3+3(NH4)2HPO4=LiCs2Y2(PO4)3+6H2O↑+0.5O2↑+6NH3↑+2NO2↑。
Preferably, the second sintering process should be carried out for more than 1 time in a temperature rise range of 500-700 ℃.
Flux and LiCs used in step 2)2Y2(PO4)3The molar ratio of the compounds is 1: 0.1-5.5; wherein the flux is made of Li2O、Cs2O and P2O5According to the molar ratio of (0.5-2) to (0-3) to (0-2).
The resulting LiCs2Y2(PO4)3The nonlinear optical crystal has the advantages of stable physical and chemical properties, moderate hardness, good mechanical properties, difficult cracking, easy processing and the like.
The third protection of the invention is that the LiCs2Y2(PO4)3The application of the nonlinear optical crystal in preparing a nonlinear optical device. The nonlinear optical device includes a laser and the like.
Preferably, the working principle of the nonlinear optical device is as follows: passing at least one beam of incident electromagnetic radiation through at least one block of LiCs2Y2(PO4)3The nonlinear optical crystal produces at least one output radiation having a frequency different from that of the incident electromagnetic radiation.
The invention has the beneficial effects that: LiCs obtained by the invention2Y2(PO4)3The nonlinear optical crystal has the advantages of short ultraviolet absorption cut-off edge, large nonlinear optical effect, stable physical and chemical properties, good mechanical properties, easy processing and the like, and can be used for manufacturing nonlinear optical devices such as laser blinding weapons, optical disc recording, laser projection televisions, optical computing, optical fiber communication and the like.
Drawings
FIG. 1 shows LiCs prepared in example 12Y2(PO4)3Polycrystalline powder and based on LiCs2Y2(PO4)3An X-ray diffraction contrast pattern simulated by the crystal structure.
FIG. 2 shows LiCs prepared in example 42Y2(PO4)3Nonlinear opticsSample pattern of the crystal.
FIG. 3 shows LiCs prepared in example 42Y2(PO4)3The structure of the crystal is shown schematically.
FIG. 4 is a graph showing the utilization of the prepared LiCs2Y2(PO4)3The crystal is made into a typical working schematic diagram of a nonlinear optical device, wherein 1 is a laser, 2 is an incident laser beam, and 3 is LiCs which is processed by crystal post-treatment and optical processing2Y2(PO4)3Crystal, 4 is the outgoing laser beam generated, 5 is a filter.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1 powdered LiCs2Y2(PO4)3Preparation of the Compounds
The preparation method adopts a solid-phase reaction method, and the reaction equation is as follows:
0.5Li2CO3+Cs2CO3+Y2O3+3NH4H2PO4=LiCs2Y2(PO4)3+1.5CO2↑+4.5H2O↑+3NH3↑。
the specific operation steps are as follows: separately weighing Li2CO30.222 g (0.003 mol)、Cs2CO31.955 g(0.006 mol)、Y2O31.355 g (0.006 mol)、NH4H2PO41.035 g (0.009 mol), placing them into a mortar, mixing and grinding them uniformly, then placing them into a corundum ceramic crucible, compacting them, placing them into a muffle furnace, heating to 500 deg.C at the speed of 10 deg.C/hr, heat-insulating and sintering for 24 hr, then cooling to room temperature, taking out, grinding them uniformly, heating to 900 deg.C at the speed of 10 deg.C/hr, sintering for 48 hr, taking out and grinding for more than 1 time midway to obtain pure phase LiCs2Y2(PO4)3A compound is provided.
As shown in fig. 1, the prepared compound has a powder X-ray diffraction pattern consistent with a pattern fitted from its single crystal structure.
Example 2 powdered LiCs2Y2(PO4)3Preparation of the Compounds
The preparation method adopts a solid-phase reaction method, and the reaction equation is as follows:
LiOH·H2O+2CsNO3+Y2O3+3(NH4)2HPO4=LiCs2Y2(PO4)3+6H2O↑+0.5O2↑+6NH3↑+2NO2↑。
the specific operation steps are as follows: respectively weighing LiOH. H2O 0.126g (0.003 mol),CsNO31.169 g(0.006 mol),Y2O30.677 g (0.003 mol),(NH4)2HPO41.188 g (0.009 mol), placing them into a mortar, mixing and grinding uniformly, then placing them into a corundum ceramic crucible, compacting them, placing them into a muffle furnace, heating to 500 deg.C at a speed of 50 deg.C/h, heat-insulating and sintering for 24 hr, then cooling to room temperature, taking out, grinding uniformly, heating to 900 deg.C at a speed of 50 deg.C/h, sintering for 48 hr, taking out and grinding for more than 1 time midway, and obtaining pure-phase LiCs2Y2(PO4)3A compound is provided.
Example 3 LiCs2Y2(PO4)3Preparation of crystals
Preparing the LiCs by growing by a melt method2Y2(PO4)3Nonlinear optical crystals, which are LiCs prepared by using example 1 or example 22Y2(PO4)3Compound and flux Li2And mixing the O according to a molar ratio of 0.1:1, placing the mixture in a crystal growth furnace, preserving the temperature of the mixture for more than 2 hours at a temperature of 700-1100 ℃ to melt the mixture into a melt, measuring the saturation temperature of the melt, cooling the melt to a temperature lower than the saturation temperature by 5 ℃, slowly cooling the melt to 600 ℃ at a speed of 0.5 ℃/day, and then rapidly cooling the melt to room temperature to obtain the crystal.
Example 4 LiCs2Y2(PO4)3Preparation of crystals
Preparing the LiCs by growing by a melt method2Y2(PO4)3Nonlinear optical crystals, which are LiCs prepared by using example 1 or example 22Y2(PO4)3The compound and the fluxing agent are mixed according to the molar ratio of 0.7:1 and then are placed in a crystal growth furnace, the mixture is kept at 700-1100 ℃ for more than 2 hours to be melted into a melt, then the saturation temperature of the melt is measured, the melt is cooled to 5 ℃ lower than the saturation temperature, then the temperature is slowly cooled to 600 ℃ at 1.5 ℃/day, and then the temperature is rapidly cooled to room temperature, so that the crystal is obtained.
The fluxing agent is made of Li2O、Cs2O and P2O5Mixing according to the molar ratio of 1:2: 1.67;
FIG. 2 shows a transparent crystal of millimeter scale grown by the method of example 4.
Testing, LiCs prepared2Y2(PO4)3The nonlinear optical crystal does not contain a symmetric center and belongs to a cubic crystal systemP2 13 space group; having a cell parameter ofa=b=c=10.5945(5)
Figure 433193DEST_PATH_IMAGE002
，α=β=γ=90.00，V=1189.16(10)
Figure DEST_PATH_IMAGE005
，ZAnd = 4. As shown in FIG. 3, the crystal has a structure of YO6Octahedron and PO4Tetrahedra connected together at vertices to form a three-dimensional framework, and Li+Ions and Cs+The ions fill the frame holes.
Subjecting the obtained LiCs to2Y2(PO4)3The non-linear optical crystal is used for diffuse reflection spectrum test, and the ultraviolet absorption cut-off of the crystal is lower than 200 nm; the crystal is not easy to break and absorb moisture.
The crystal of the invention has frequency doubling effect. FIG. 4 shows a hair-dryerPrepared LiCs2Y2(PO4)3The structure of the nonlinear optical device manufactured by the crystal is shown schematically. YAG laser as base frequency light source at room temperature, laser 1 emits incident laser beam 2 (near infrared light with incident wavelength of 1064 nm) to penetrate into LiCs2Y2(PO4)3The crystal 3 generates an outgoing laser beam 4 (green laser with an output wavelength of 532 nm) which passes through a filter 5 to obtain a desired laser beam having an intensity corresponding to KH2PO40.9 times of. The nonlinear optical laser can be a frequency doubling generator or an upper and a lower frequency converter or an optical parametric oscillator, etc.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (4)

1. LiCs2Y2(PO4)3A nonlinear optical crystal characterized by: said LiCs2Y2(PO4)3The nonlinear optical crystal does not contain a symmetric center and belongs to a cubic crystal systemP213 space group with cell parameters ofa=b=c=10.5945(5)
Figure DEST_PATH_IMAGE002
，α=β=γ=90.00，V=1189.16(10)
Figure DEST_PATH_IMAGE004
，Z=4；
The preparation method comprises the following steps:
1) uniformly mixing a Li-containing compound, a Cs-containing compound, a Y-containing compound and a P-containing compound according to the stoichiometric ratio of Li, Cs, Y and P of 1:2:2:3, heating to 400-500 ℃ at the speed of 10-200 ℃/h, carrying out heat preservation sintering for 12-72 hours, cooling to room temperature, taking out, grinding uniformly, heating to 500-1100 ℃ at the speed of 10-200 ℃/h, and sintering for 24-72 hours to obtain LiCs2Y2(PO4)3Powder;
2) fluxing agent and the obtained LiCs2Y2(PO4)3Mixing the powder, placing the mixture in a crystal growth furnace, heating to 700-1200 ℃ to melt the mixture into a melt, measuring the saturation temperature of the melt, cooling the melt to 5-15 ℃ below the saturation temperature, slowly cooling to 600 ℃ at the speed of 0.5-10 ℃/day, and then rapidly cooling to room temperature to obtain LiCs2Y2(PO4)3A nonlinear optical crystal;
wherein the flux is made of Li2O、Cs2O and P2O5According to the molar ratio of (0.5-2) to (0-3) to (0-2).
2. LiCS according to claim 12Y2(PO4)3A nonlinear optical crystal characterized by: the Li-containing compound in the step 1) is Li2CO3Or LiOH. H2O; the Cs-containing compound is Cs2CO3Or CsNO3(ii) a The compound containing Y is Y2O3(ii) a The P-containing compound is NH4H2PO4Or (NH)4)2HPO4。
3. LiCS according to claim 12Y2(PO4)3A nonlinear optical crystal characterized by: flux and LiCs used in step 2)2Y2(PO4)3The molar ratio of the powder is 1: 0.1-5.5.
4. LiCS according to claim 12Y2(PO4)3The application of the nonlinear optical crystal in preparing a nonlinear optical device.
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CN110079858B (en) * 2019-05-20 2020-11-27 闽江学院 Cesium magnesium sulfate nonlinear optical crystal and preparation method and application thereof
CN110079861B (en) * 2019-06-14 2022-02-15 山东大学 Yttrium strontium phosphate crystal and preparation method and application thereof

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CN101831706A (en) * 2009-03-13 2010-09-15 中国科学院福建物质结构研究所 Growth method of low ultraviolet absorption YA13(BO3)4 crystal
CN105839185A (en) * 2016-05-16 2016-08-10 中国科学院福建物质结构研究所 Cs2LiPO4 compound and Cs2LiPO4 nonlinear optical crystal as well as preparation method and application thereof
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