CN115467023A - Compound lithium gallium iodine oxygen and sodium gallium iodine oxygen, lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystal, and preparation method and application thereof - Google Patents
Compound lithium gallium iodine oxygen and sodium gallium iodine oxygen, lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystal, and preparation method and application thereof Download PDFInfo
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- CN115467023A CN115467023A CN202211252668.6A CN202211252668A CN115467023A CN 115467023 A CN115467023 A CN 115467023A CN 202211252668 A CN202211252668 A CN 202211252668A CN 115467023 A CN115467023 A CN 115467023A
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- gallium
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- oxygen
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- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 156
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 137
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 118
- 239000011734 sodium Substances 0.000 title claims abstract description 118
- 150000001875 compounds Chemical class 0.000 title claims abstract description 91
- 239000013078 crystal Substances 0.000 title claims abstract description 86
- PRXLCSIMRQFQMX-UHFFFAOYSA-N [O].[I] Chemical compound [O].[I] PRXLCSIMRQFQMX-UHFFFAOYSA-N 0.000 title claims abstract description 80
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 69
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 64
- 230000003287 optical effect Effects 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 43
- -1 polytetrafluoroethylene Polymers 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 24
- 229910052740 iodine Inorganic materials 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 18
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 17
- 239000011630 iodine Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 3
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 3
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 3
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 claims description 3
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910002601 GaN Inorganic materials 0.000 claims description 2
- 229910005540 GaP Inorganic materials 0.000 claims description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 2
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 238000004891 communication Methods 0.000 claims description 2
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 6
- 150000003388 sodium compounds Chemical class 0.000 claims 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims 4
- WBPWDGRYHFQTRC-UHFFFAOYSA-N 2-ethoxycyclohexan-1-one Chemical compound CCOC1CCCCC1=O WBPWDGRYHFQTRC-UHFFFAOYSA-N 0.000 claims 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 2
- 230000005670 electromagnetic radiation Effects 0.000 claims 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims 2
- SYWXNZXEJFSLEU-UHFFFAOYSA-M lithium;periodate Chemical compound [Li+].[O-]I(=O)(=O)=O SYWXNZXEJFSLEU-UHFFFAOYSA-M 0.000 claims 2
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 claims 2
- 239000001632 sodium acetate Substances 0.000 claims 2
- 235000017281 sodium acetate Nutrition 0.000 claims 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 2
- 239000011780 sodium chloride Substances 0.000 claims 2
- 239000011775 sodium fluoride Substances 0.000 claims 2
- 235000013024 sodium fluoride Nutrition 0.000 claims 2
- 239000011697 sodium iodate Substances 0.000 claims 2
- 235000015281 sodium iodate Nutrition 0.000 claims 2
- 229940032753 sodium iodate Drugs 0.000 claims 2
- 239000004317 sodium nitrate Substances 0.000 claims 2
- 235000010344 sodium nitrate Nutrition 0.000 claims 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 2
- 235000011152 sodium sulphate Nutrition 0.000 claims 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 230000005855 radiation Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 23
- 239000002994 raw material Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 8
- 238000002083 X-ray spectrum Methods 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000010431 corundum Substances 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- XCZLSTLZPIRTRY-UHFFFAOYSA-N oxogallium Chemical compound [Ga]=O XCZLSTLZPIRTRY-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 230000001427 coherent effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical class OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
- C30B7/04—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent using aqueous solvents
-
- 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
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
-
- 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
- G02F1/353—Frequency conversion, i.e. wherein a light beam is generated with frequency components different from those of the incident light beams
-
- 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
-
- 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
- G02F1/39—Non-linear optics for parametric generation or amplification of light, infrared or ultraviolet waves
Abstract
The invention relates to compounds of lithium gallium oxyiodide and sodium gallium oxyiodide and lithium gallium oxyiodide and sodium gallium oxyiodide nonlinear optical crystals, a preparation method and application thereof, wherein the chemical general formulas of the compounds and the crystals are AGa (IO) 3 ) 4 Wherein A = Li, na, both belonging to monoclinic system, space group P2 1 Cell parameterIs composed of
c =10.502 (5) -11.335 (4), α =90 °, β =90.255 (17) ° -91.850 (14), γ =90 °, Z =2, and molecular weights 776.26 and 792.31, respectively. The compounds lithium gallium iodine oxygen and sodium gallium iodine oxygen are prepared by a hydrothermal method and a solid-phase reaction method, the lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystal grows by the hydrothermal method, the solid-phase reaction method or a solution method, and the obtained product is directly a crystal. The series of materials can be used for manufacturing a second harmonic generator, an upper frequency converter, a lower frequency converter, an optical parametric oscillator and the like.
Description
Technical Field
The invention relates to nonlinear optical crystals of compounds of lithium gallium oxyiodide, sodium gallium oxyiodide and lithium gallium oxyiodide and sodium gallium oxyiodide, wherein the molecular general formulas of the compounds of lithium gallium oxyiodide, sodium gallium oxyiodide and lithium gallium oxyiodide and sodium gallium oxyiodide are AGa (IO) 3 ) 4 Wherein a = Li, na, a method of making the crystal and a nonlinear optical device made using the crystal.
Background
Mid-far infrared coherent light with wavelengths between 3 and 14 μm is becoming increasingly important for its potential applications in semiconductor lithography, laser micromachining and modern scientific instrumentation. For a solid-state laser, the medium-far infrared coherent light is obtained by a cascade frequency conversion technology of a nonlinear optical crystal. However, for a suitable mid-far infrared nonlinear optical crystal, it must meet the following stringent structural and performance requirements, including i) non-centrosymmetric structures; ii) large second order nonlinear optical coefficient (d) ij ) At least d with KDP 36 Equivalent; iii) High transparency in the mid-and far-infrared region; iv) medium birefringence (Δ n = 0.03-0.1) to satisfy the phase matching condition for the generation of middle and far infrared second harmonics; v) easy preparation, no toxicity, chemical stability and good mechanical properties. However, the properties contradict each other, and the large bandgap material tends to show smaller frequency multiplication response and birefringence, so that designing and synthesizing mid-far infrared nonlinear optical crystals remains a great challenge.
Metallic iodates are promising candidates for mid-infrared NLO applications because they have been widely studied with their broad transparency from the visible region to the far infrared (12.5 μm), wider band gap, and higher laser damage threshold. Due to I V Stereo-chemically active lone pair of electrons, IO, on the ion 3 The unit is a good NLO activityAnionic groups with greater microscopic secondary NLO sensitivity, arranging IOs in a polar or non-centrosymmetric (NCS) crystal structure 3 The unit can generate a crystal with excellent Second Harmonic Generation (SHG) performance, and is a candidate for synthesizing NLO crystal materials.
Disclosure of Invention
One of the objects of the present invention is to provide compounds of lithium gallium iodoxy and sodium gallium iodoxy and a method for preparing the same.
The other purpose of the invention is to provide a lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystal and a preparation method thereof.
The invention also aims to provide application of the lithium gallium oxyiodide and sodium gallium oxyiodide nonlinear optical crystal.
One of the objects of the invention is achieved by:
the invention aims to provide compounds of lithium gallium iodoxy and sodium gallium iodoxy, which are characterized in that the chemical formulas of the compounds of lithium gallium iodoxy and sodium gallium iodoxy are AGa (IO) 3 ) 4 Wherein a = Li, na, molecular weight 776.26 and 792.31. Preparing compounds of lithium gallium iodoxy and sodium gallium iodoxy by a hydrothermal method or a solid-phase reaction method according to the following chemical reaction formulas:
1)A 2 CO 3 (A＝Li，Na)+Ga 2 O 3 +8HIO 3 →2AGa(IO 3 ) 4 (A＝Li，Na)+4H 2 O↑+CO 2 ↑
2)2AOH(A＝Li，Na)+Ga 2 O 3 +8HIO 3 →2AGa(IO 3 ) 4 (A＝Li，Na)+5H 2 O↑
3)2AF(A＝Li，Na)+Ga 2 O 3 +8HIO 3 →2AGa(IO 3 ) 4 (A＝Li，Na)+3H 2 O↑+2HF↑
4)2ACl(A＝Li，Na)+Ga 2 O 3 +8HIO 3 →2AGa(IO 3 ) 4 (A＝Li，Na)+3H 2 O↑+2HCl↑
5)A 2 CO 3 (A＝Li，Na)+2GaCl 3 +8HIO 3 →2AGa(IO 3 ) 4 (A＝Li，Na)+6HCl↑+CO 2 ↑+H 2 O↑
6)AOH(A＝Li，Na)+GaCl 3 +4HIO 3 →AGa(IO 3 ) 4 (A＝Li，Na)+H 2 O↑+3HCl↑
7)AF(A＝Li，Na)+GaCl 3 +4HIO 3 →AGa(IO 3 ) 4 (A＝Li，Na)+3HCl↑+HF↑
8)ACl(A＝Li，Na)+GaCl 3 +4HIO 3 →2AGa(IO 3 ) 4 (A＝Li，Na)+4HCl↑
9)A 2 CO 3 (A＝Li，Na)+Ga 2 O 3 +4I 2 O 5 →2AGa(IO 3 ) 4 (A＝Li，Na)+CO 2 ↑
10)2AF(A＝Li，Na)+Ga 2 O 3 +4I 2 O 5 +H 2 O→2AGa(IO 3 ) 4 (A＝Li，Na)+2HF↑
11)A 2 CO 3 (A＝Li，Na)+Ga 2 O 3 +8H 5 IO 6 →2AGa(IO 3 ) 4 (A＝Li，Na)+20H 2 O↑+CO 2 ↑+4O 2 ↑
12)2AF(A＝Li，Na)+Ga 2 O 3 +8H 5 IO 6 →2AGa(IO 3 ) 4 (A＝Li，Na)+19H 2 O↑+2HF↑+4O 2 ↑
the second purpose of the invention is realized by the following steps:
the invention aims to provide a lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystal which is characterized in that the chemical formula of the lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystal is AGa (IO) 3 ) 4 Wherein A = Li, na, does not have a center of symmetry, belongs to the monoclinic system, space group P2 1 Cell parameter of
c =10.502 (5) -11.335 (4), α =90 °, β =90.255 (17) ° -91.850 (14), γ =90 °, Z =2. Growing the nonlinear optical crystal of lithium gallium iodine oxygen and sodium gallium iodine oxygen by a hydrothermal method, a solid-phase reaction method or a solution method.
The hydrothermal method is used for growing lithium gallium iodideOxygen and sodium gallium iodine oxygen nonlinear optical crystal with molecular formula of LiGa (IO) respectively 3 ) 4 And NaGa (IO) 3 ) 4 The specific operation is carried out according to the following steps:
a. adding a compound containing A = Li and Na, a gallium-containing compound and an iodine-containing compound into a polytetrafluoroethylene lining of a high-pressure reaction kettle, adding 0.1-50mL of deionized water or 0.1-50g of a mineralizer, and fully and uniformly mixing to obtain a mixed solution, wherein the molar ratio of the compound containing A = Li to the compound containing Ga to the compound containing iodine is 0-2.
b. And (b) screwing the cover of the polytetrafluoroethylene lining where the mixed solution is located in the step (a), then putting the cover into a corresponding high-pressure reaction kettle, and screwing the piston of the reaction kettle.
c. And c, placing the high-pressure reaction kettle in the step b in a constant temperature box, heating to 120-330 ℃, keeping the temperature for a period of time, and cooling to room temperature.
d. And opening the high-pressure reaction kettle, and filtering the solution containing the crystals to obtain the transparent lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystals.
The solid phase reaction method is used for growing AGa (IO) 3 ) 4 Wherein A = Li, na nonlinear optical crystal, the specific operation is carried out according to the following steps:
uniformly mixing compound lithium gallium iodine oxygen and sodium gallium iodine oxygen single-phase polycrystalline powder with a fluxing agent, heating the mixture to the temperature of 150-500 ℃, keeping the temperature for a long time, and cooling to room temperature, wherein the molar ratio of the compound lithium gallium iodine oxygen and sodium gallium iodine oxygen single-phase polycrystalline powder to the fluxing agent is 1;
or directly heating a mixture of A = Li, na compound, gallium-containing compound and iodine-containing compound or a mixture of A = Li, na compound, gallium-containing compound and iodine-containing compound and fluxing agent to 150-500 ℃, keeping the temperature for a long time, and cooling to room temperature, wherein the molar ratio of A = Li, na compound, gallium-containing compound and iodine-containing compound to fluxing agent is 0-2;
the fluxing agent mainly comprises alkali metal salts, namely alkali metal carbonate, alkali metal nitrate, alkali metal sulfate, alkali metal oxalate, alkali metal borate, alkali metal phosphate, alkali metal halide, alkali metal iodate, alkali metal periodate and alkali metal oxide, alkali metal hydroxide, and at least one or more of gallium oxide, gallium chloride, gallium nitride, gallium arsenide, gallium phosphide, gallium sulfide, iodic acid, diiodo pentoxide and periodic acid.
The method for growing the lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystal by the solution method comprises the following specific steps:
adding the A = Li-containing, na-containing compound, gallium-containing compound and iodine-containing compound into a beaker, adding 0.1-400mL of deionized water, and stirring the solution until the solution is clear. And then placing the beaker on a heating table, heating to 25-400 ℃, and obtaining the lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystal after a period of time. To further grow it, seeds of the series of crystals were suspended in solution with a fine platinum wire. To reduce the evaporation of water, the beaker was covered with a polyethylene sheet and perforated with tens of mm-sized holes. And after a period of time, taking the lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystal out of the solution.
The third purpose of the invention is realized by the following steps:
the lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystal is suitable for middle and far infrared band laser frequency conversion devices, infrared communication devices and infrared laser guidance devices, and is used for preparing nonlinear optical devices such as secondary harmonic generators, upper or lower frequency converters or optical parametric oscillators.
Drawings
FIG. 1 is a theoretical X-ray spectrum of a compound Li-Ga-I-O crystal prepared in the present invention
FIG. 2 is a theoretical X-ray spectrum of a compound Na-Ga-O crystal prepared by the present invention
FIG. 3 shows AGa (IO) of the present invention 3 ) 4 Wherein a = Li, na crystal structure diagram;
FIG. 4 is a diagram of nonlinear optical effects of Li-Ga-O-I and Na-Ga-O-I crystals as frequency doubling crystals. Wherein 1 is a mirror, 2 is a Q-switch, 3 is a polarizer, 4 is Nd: YAG,5 is an OPO input mirror, 6KTP crystal, OPO output mirror and total reflection mirror with 1064nm wavelength 7, 2.1 micron wavelength light reflection mirror 8, AGa (IO) after crystal post-treatment and optical processing 9 3 ) 4 Where a = Li, na single crystal, 10 is the outgoing laser beam generated.
Detailed Description
The invention is explained in more detail below with reference to the drawing and the exemplary embodiments, but is not limited to the exemplary embodiments. Any modifications and variations made on the basis of the present invention are intended to be within the scope of the present invention.
Example 1
According to the reaction formula: a. The 2 CO 3 (A＝Li，Na)+Ga 2 O 3 +8HIO 3 →2AGa(IO 3 ) 4 (A＝Li，Na)+4H 2 O↑+CO 2 ↑, synthetic AGa (IO) 3 ) 4 (a = Li, na) compound:
a. a is to be 2 CO 3 (A＝Li，Na)、Ga 2 O 3 、HIO 3 Directly weighing raw materials according to a molar ratio of 1;
b. b, screwing a polytetrafluoroethylene lining cover in which the mixed liquid is located in the step a, then putting the polytetrafluoroethylene lining cover into a clean and pollution-free high-pressure reaction kettle, and screwing a piston of the reaction kettle;
c. placing the high-pressure reaction kettle in the step 5 in a constant temperature box, heating to 120 ℃ at the heating rate of 10 ℃/h, keeping the temperature for 10 days, and cooling to room temperature at the cooling rate of 3 ℃/h;
d. and opening the high-pressure reaction kettle, and filtering the solution containing the crystals to obtain compounds of lithium gallium oxyiodide and sodium gallium oxyiodide, wherein the obtained product is a transparent crystal.
Example 2
According to the reaction formula: 2AOH (a = Li, na) + Ga 2 O 3 +8HIO 3 →2AGa(IO 3 ) 4 (A＝Li，Na)+5H 2 O ↓, synthetic AGa (IO) 3 ) 4 (a = Li, na) compound:
a. mixing AOH (A = Li, na), ga 2 O 3 、HIO 3 Directly weighing raw materials according to a molar ratio of 2;
b. b, screwing the polytetrafluoroethylene lining cover in which the mixed solution is located in the step a, then putting the polytetrafluoroethylene lining cover into a clean and pollution-free high-pressure reaction kettle, and screwing the piston of the reaction kettle;
c. placing the high-pressure reaction kettle in the step 5 in a constant temperature box, heating to 220 ℃ at a heating rate of 10 ℃/h, keeping the temperature for 10 days, and cooling to room temperature at a cooling rate of 3 ℃/h;
d. opening the high-pressure reaction kettle, and filtering the solution containing the crystals to obtain the compounds of lithium gallium iodine oxygen and sodium gallium iodine oxygen, wherein the obtained products are transparent crystals.
Example 3
According to the reaction formula: AF (a = Li, na) + GaCl 3 +4HIO 3 →AGa(IO 3 ) 4 (A = Li, na) +3HCl ↓ + HF [% ] and synthetic AGa (IO) 3 ) 4 (a = Li, na) compound:
a. mixing AF (A = Li, na) and Ga 2 O 3 、HIO 3 Directly weighing raw materials according to a molar ratio of 1;
b. b, screwing a polytetrafluoroethylene lining cover in which the mixed liquid is located in the step a, then putting the polytetrafluoroethylene lining cover into a clean and pollution-free high-pressure reaction kettle, and screwing a piston of the reaction kettle;
c. placing the high-pressure reaction kettle in the step 5 in a constant temperature box, heating to 330 ℃ at a heating rate of 10 ℃/h, keeping the temperature for 10 days, and cooling to room temperature at a cooling rate of 3 ℃/h;
d. and opening the high-pressure reaction kettle, and filtering the solution containing the crystals to obtain compounds of lithium gallium oxyiodide and sodium gallium oxyiodide, wherein the obtained product is a transparent crystal.
Example 4
According to the reaction formula:2AF(A＝Li，Na)+Ga 2 O 3 +4I 2 O 5 +H 2 O→2AGa(IO 3 ) 4 (A = Li, na) +2HF ≠ synthesized AGa (IO) 3 ) 4 (a = Li, na) compound:
a. mixing AF (A = Li, na) and Ga 2 O 3 、I 2 O 5 Directly weighing raw materials according to a molar ratio of 5;
b. b, screwing a polytetrafluoroethylene lining cover in which the mixed liquid is located in the step a, then putting the polytetrafluoroethylene lining cover into a clean and pollution-free high-pressure reaction kettle, and screwing a piston of the reaction kettle;
c. placing the high-pressure reaction kettle in the step 5 in a constant temperature box, heating to 180 ℃ at the heating rate of 10 ℃/h, keeping the temperature for 10 days, and cooling to room temperature at the cooling rate of 3 ℃/h;
d. opening the high-pressure reaction kettle, and filtering the solution containing the crystals to obtain the compounds of lithium gallium iodine oxygen and sodium gallium iodine oxygen, wherein the obtained products are transparent crystals.
Example 5
According to the reaction formula: 2AF (a = Li, na) + Ga 2 O 3 +8H 5 IO 6 →2AGa(IO 3 ) 4 (A＝Li，Na)+19H 2 O↑+2HF↑+4O 2 Synthesis of AGa (IO) 3 ) 4 (a = Li, na) compound:
a. mixing AF (A = Li, na) and Ga 2 O 3 、H 5 IO 6 Directly weighing raw materials according to a molar ratio of 2;
b. b, screwing the polytetrafluoroethylene lining cover in which the mixed solution is located in the step a, then putting the polytetrafluoroethylene lining cover into a clean and pollution-free high-pressure reaction kettle, and screwing the piston of the reaction kettle;
c. placing the high-pressure reaction kettle in the step 5 in a constant temperature box, heating to 300 ℃ at the heating rate of 10 ℃/h, keeping the temperature for 10 days, and cooling to room temperature at the cooling rate of 3 ℃/h;
d. and opening the high-pressure reaction kettle, and filtering the solution containing the crystals to obtain compounds of lithium gallium oxyiodide and sodium gallium oxyiodide, wherein the obtained product is a transparent crystal.
Example 6
According to the reaction formula A 2 CO 3 (A＝Li，Na)+Ga 2 O 3 +8HIO 3 →2AGa(IO 3 ) 4 (A＝Li，Na)+4H 2 O↑+CO 2 ×) synthetic AGa (IO 3 ) 4 (a = Li, na) compound:
a is to be 2 CO 3 (A＝Li，Na)、Ga 2 O 3 、HIO 3 Weighing according to a molar ratio of 1 3 ) 4 The X-ray spectra obtained for the (a = Li, na) single crystal structure are consistent;
mixing the obtained compounds lithium gallium iodine oxygen and sodium gallium iodine oxygen, AGa (IO) 3 ) 4 (A = Li, na), filling the single-phase polycrystalline powder into an open corundum crucible with the diameter phi of 100mm multiplied by 100mm, keeping the temperature at 150 ℃ for 120 hours, and cooling the single-phase polycrystalline powder to room temperature at the cooling rate of 2 ℃/h to obtain lithium gallium oxyiodide and sodium gallium oxyiodide crystals;
example 7
According to the reaction formula: 2AOH (a = Li, na) + Ga 2 O 3 +8HIO 3 →2AGa(IO 3 ) 4 (A＝Li，Na)+5H 2 O ← R, synthetic AGa (IO) 3 ) 4 (a = Li, na) compound:
AOH (A = Li, na), ga 2 O 3 、HIO 3 Weighing according to a molar ratio of 2Mixing, grinding, placing into an open corundum crucible of phi 100mm × 100mm, placing into a muffle furnace, slowly heating to 350 deg.C, holding the temperature for 24 hr, cooling to room temperature, taking out, grinding for the second time, placing into the muffle furnace, heating to 400 deg.C, holding the temperature for 24 hr, cooling to room temperature, taking out, grinding for the third time, placing into a muffle furnace, keeping the temperature at 500 deg.C for 24 hr, taking out, grinding to obtain single-phase polycrystalline powder of compounds Li-Ga-I-O and Na-Ga-I-O, and analyzing the product with X-ray to obtain X-ray spectrogram and compounds Li-Ga-I-O and Na-Ga-I-O, AGa (IO) 3 ) 4 (a = Li, na), the single crystal structure gives a uniform X-ray spectrum;
mixing the obtained compounds lithium gallium iodine oxygen and sodium gallium iodine oxygen, AGa (IO) 3 ) 4 (A = Li, na), filling the single-phase polycrystalline powder into an open corundum crucible with the diameter phi of 100mm multiplied by 100mm, keeping the temperature at 500 ℃ for 120 hours, and cooling the single-phase polycrystalline powder to room temperature at the cooling rate of 2 ℃/h to obtain lithium gallium oxyiodide and sodium gallium oxyiodide crystals;
example 8
According to the reaction formula: 2AF (a = Li, na) + Ga 2 O 3 +8HIO 3 →2AGa(IO 3 ) 4 (A＝Li，Na)+3H 2 O ↓ +2HF × (IO) synthesized AGa 3 ) 4 (a = Li, na) compound:
mixing AF (A = Li, na) and Ga 2 O 3 、HIO 3 Weighing and placing the materials into a mortar according to the molar ratio of 2 3 ) 4 (a = Li, na), the X-ray spectra obtained for the single crystal structure are consistent;
the obtained compound is lithium gallium iodine oxygen andsodium gallium iodine oxygen, AGa (IO) 3 ) 4 (A = Li, na), filling the single-phase polycrystalline powder into an open corundum crucible with the diameter of phi 100mm multiplied by 100mm, keeping the temperature at 450 ℃ for 120 hours, and cooling the single-phase polycrystalline powder to room temperature at the cooling rate of 2 ℃/h to obtain lithium gallium oxygen iodide and sodium gallium oxygen iodide crystals;
example 9
According to the reaction formula: 2ACl (a = Li, na) + Ga 2 O 3 +8HIO 3 →2AGa(IO 3 ) 4 (A＝Li，Na)+3H 2 O ↓ +2HCl [ ° H, synthetic AGa (IO) 3 ) 4 (a = Li, na) compound:
mixing ACL (A = Li, na) and Ga 2 O 3 、HIO 3 Weighing and placing the materials into a mortar according to the molar ratio of 2 3 ) 4 (a = Li, na), the X-ray spectra obtained for the single crystal structure are consistent;
mixing the obtained compounds lithium gallium iodoxy and sodium gallium iodoxy, AGa (IO) 3 ) 4 (A = Li, na), filling the single-phase polycrystalline powder into an open corundum crucible with the diameter of phi 100mm multiplied by 100mm, keeping the temperature constant at 300 ℃ for 120 hours, and cooling the single-phase polycrystalline powder to room temperature at the cooling rate of 2 ℃/h to obtain lithium gallium oxygen iodide and sodium gallium oxygen iodide crystals;
example 10
According to the reaction formula: a. The 2 CO 3 (A＝Li，Na)+2GaCl 3 +8HIO 3 →2AGa(IO 3 ) 4 (A＝Li，Na)+6HCl↑+CO 2 ↑+H 2 O ↓, synthetic AGa (IO) 3 ) 4 (a = Li, na) compound:
a is prepared from 2 CO 3 (A＝Li，Na)、GaCl 3 、HIO 3 The raw materials are directly weighed according to the mol ratio of 1. And then placing the beaker on a heating table, heating to 400 ℃, and obtaining the lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystal after 7 days. To further grow it, a seed crystal of the series of crystals was suspended in solution with a thin platinum wire. To reduce the evaporation of water, the beaker was covered with a polyethylene sheet and perforated with tens of mm-sized holes. After 3 weeks, the larger lithium gallium iodoxy and sodium gallium iodoxy nonlinear optical crystals were removed from the solution.
Example 11
According to the reaction formula: AOH (A = Li, na) + GaCl 3 +4HIO 3 →AGa(IO 3 ) 4 (A＝Li，Na)+H 2 O ↓ +3HCl [ ° H, synthetic AGa (IO) 3 ) 4 (a = Li, na) compound:
AOH (A = Li, na), gaCl 3 、HIO 3 The raw materials are directly weighed according to the mol ratio of 1. And then placing the beaker on a heating table, heating to 300 ℃, and obtaining the lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystal after 7 days. To further grow it, seeds of the series of crystals were suspended in solution with a fine platinum wire. To reduce the evaporation of water, the beaker was covered with a polyethylene sheet and perforated with tens of mm-sized holes. After 5 weeks, the larger lithium gallium iodoxy and sodium gallium iodoxy nonlinear optical crystals were removed from the solution.
Example 12
According to the reaction formula: AF (a = Li, na) + GaCl 3 +4HIO 3 →AGa(IO 3 ) 4 (A = Li, na) +3HCl ≠ + HF ≠ ℃, (IO) synthesized AGa 3 ) 4 (a = Li, na) compound:
mixing AF (A = Li, na), gaCl 3 、HIO 3 The raw materials are directly weighed according to the mol ratio of 1. Then placing the beaker on a heating table, heating to 150 ℃, and obtaining the lithium gallium after 12 daysIodine oxygen and sodium gallium iodine oxygen nonlinear optical crystals. To further grow it, seeds of the series of crystals were suspended in solution with a fine platinum wire. To reduce the evaporation of water, the beaker was covered with a polyethylene sheet and perforated with holes of several tens of millimeters. After 4 weeks, the larger lithium gallium iodoxy and sodium gallium iodoxy nonlinear optical crystals were removed from the solution.
Example 13
According to the reaction formula: ACl (a = Li, na) + GaCl 3 +4HIO 3 →2AGa(IO 3 ) 4 (A = Li, na) +4HCl ≠ synthesized AGa (IO) 3 ) 4 (a = Li, na) compound:
mixing ACI (A = Li, na), gaCl 3 、HIO 3 The raw materials are directly weighed according to the mol ratio of 1. And then placing the beaker on a heating table, heating to 25 ℃, and obtaining the lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystal after 9 days. To further grow it, seeds of the series of crystals were suspended in solution with a fine platinum wire. To reduce the evaporation of water, the beaker was covered with a polyethylene sheet and perforated with tens of mm-sized holes. After 5 weeks, the larger lithium gallium iodoxy and sodium gallium iodoxy nonlinear optical crystals were removed from the solution.
Example 14
Processing a frequency doubling device with the size of 5mm multiplied by 6mm by any lithium gallium iodine oxygen crystal and sodium gallium iodine oxygen crystal obtained in the examples 1 to 13 according to the matching direction, placing the processed frequency doubling device at the position of 9 in the device shown in the figure 4, and adjusting Q Nd at room temperature; an OPO is additionally arranged outside a YAG laser as an input light source, the incident wavelength is 2100nm, and the frequency doubling light output of 1050nm is received through a photomultiplier tube.
Claims (10)
1. The compounds are lithium gallium iodine oxygen and sodium gallium iodine oxygen, and are characterized in that the molecular general formulas of the compounds are AGa (IO) 3 ) 4 Wherein A = Li or Na, and molecular formula is LiGa (IO) respectively 3 ) 4 And NaGa (IO) 3 ) 4 The molecular weights are 776.26 and 792.31, respectively.
2. The compounds Li-Ga-O-and Na-Ga-O-as claimed in claim 1, wherein the compounds are prepared by hydrothermal or solid-phase reaction.
3. The method for preparing the compounds of lithium gallium ioxoxide and sodium gallium ioxoxide according to claim 2, characterized in that:
the hydrothermal method is used for preparing compounds of lithium gallium oxyiodide and sodium gallium oxyiodide as follows: adding a lithium or sodium compound, a gallium-containing compound and an iodine-containing compound into a polytetrafluoroethylene lining of a high-pressure reaction kettle, adding deionized water and a mineralizer, and fully and uniformly mixing to obtain a mixed solution, wherein the molar ratio of the lithium or sodium compound to the gallium-containing compound to the iodine-containing compound to the mineralizer is 0-2;
the solid-phase reaction method for preparing the compounds of lithium gallium oxyiodide and sodium gallium oxyiodide comprises the following specific operations: uniformly mixing a lithium or sodium compound, a gallium-containing compound and an iodine-containing compound, grinding, putting into a muffle furnace, and calcining, wherein the single-phase polycrystalline powder of the compounds lithium gallium iodoxy and sodium gallium iodoxy is prepared through grinding and calcining for multiple times, wherein the molar ratio of the lithium or sodium compound to the gallium-containing compound to the iodine-containing compound is 0-2;
wherein the number of moles of the lithium-or sodium-containing compound is based on the number of moles of the lithium element contained therein; the number of moles of the gallium-containing compound is calculated by the number of moles of the gallium element contained therein; the number of moles of the iodine-containing compound is calculated by the number of moles of iodine elements contained in the iodine-containing compound;
the lithium or sodium containing compound comprises at least one of lithium hydroxide or sodium hydroxide, lithium oxide or sodium oxide and alkali metal salts, wherein the alkali metal salts comprise lithium fluoride or sodium fluoride, lithium chloride or sodium chloride, lithium bromide or sodium bromide, lithium nitrate or sodium nitrate, lithium acetate or sodium acetate, lithium carbonate or sodium carbonate, lithium sulfate or sodium sulfate;
the gallium-containing compound comprises one or more of metal gallium, gallium oxide, gallium chloride, gallium nitride, gallium arsenide, gallium phosphide and gallium sulfide;
the iodine-containing compound comprises one or two of diiodide, iodic acid, periodic acid, lithium iodate, lithium periodate, sodium iodate and sodium periodate.
4. The nonlinear optical crystal of lithium gallium iodine oxygen and sodium gallium iodine oxygen is characterized in that the chemical general formulas of the two crystals are AGa (IO) 3 ) 4 Wherein A = Li or Na, both belonging to the monoclinic system, space group P2 1 Cell parameter of
c＝10.502(5)-11.335(4),α＝90°,β＝90.255(17)°-91.850(14),γ＝90°，Z＝2。
5. The nonlinear optical crystal of lithium gallium ioxode and sodium gallium ioxode as claimed in claim 4, wherein the nonlinear optical crystal of lithium gallium ioxode and sodium gallium ioxode is grown by hydrothermal method and solution method.
6. The method for preparing a nonlinear optical crystal of lithium gallium ioxoxide and sodium gallium ioxoxide according to claim 5, characterized in that:
the specific operation of the hydrothermal method for growing the lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystal is as follows: adding the compound lithium gallium iodine oxygen and sodium gallium iodine oxygen single-phase polycrystalline powder obtained in the claim 1 or the mixture of the compound lithium gallium iodine oxygen and sodium gallium iodine oxygen single-phase polycrystalline powder obtained in the claim 1 and a mineralizer, or directly adding the mixture of a lithium or sodium compound, a gallium-containing compound and an iodine-containing compound or a lithium or sodium-containing compound, a gallium-containing compound and an iodine-containing compound and a mineralizer into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and adding deionized water to fully and uniformly mix the mixture to obtain a mixed solution; putting the polytetrafluoroethylene lining into an autoclave, putting the autoclave into a thermostat, heating, cooling to room temperature, and filtering a solution containing crystals to obtain transparent lithium gallium iodine oxygen or sodium gallium iodine oxygen nonlinear optical crystals;
the specific operation of the solution method for growing the lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystal is as follows: adding the compound lithium gallium iodine oxygen and sodium gallium iodine oxygen single-phase polycrystalline powder obtained in claim 1 or the compound lithium gallium iodine oxygen and sodium gallium iodine oxygen single-phase polycrystalline powder obtained in claim 1 and a fluxing agent into a beaker, adding deionized water for dissolving, stirring the solution until the solution is clear, then placing the beaker into the air, evaporating the solution, and growing the lithium gallium iodine oxygen or sodium gallium iodine oxygen nonlinear optical crystal.
7. The process according to claim 6, wherein the molar ratio of the compound lithium gallium iodine oxygen and sodium gallium iodine oxygen single-phase polycrystalline powder to the mineralizer is 1; or wherein the molar ratio of lithium or sodium containing compound, gallium containing compound and iodine containing compound to mineralizer is 0-2; the mineralizer comprises at least one or more of lithium hydroxide or sodium hydroxide, lithium oxide or sodium oxide, lithium fluoride or sodium fluoride, lithium chloride or sodium chloride, lithium bromide or sodium bromide, lithium nitrate or sodium nitrate, lithium acetate or sodium acetate, lithium carbonate or sodium carbonate, lithium sulfate or sodium sulfate, lithium iodate or sodium iodate, lithium periodate or sodium periodate, diiodo pentoxide, periodic acid, iodic acid, gallium oxide, gallium chloride.
8. A nonlinear optical device comprising means for passing at least one beam of incident electromagnetic radiation through at least one nonlinear optical crystal to produce at least one output radiation having a frequency different from the incident electromagnetic radiation, wherein: wherein the nonlinear optical crystal is lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystal AGa (IO) 3 ) 4 Wherein a = Li or Na.
9. The lithium gallium iodine oxygen and sodium gallium iodine oxygen nonlinear optical crystal according to claim 4 is used for preparing multiband frequency doubling devices or optical elements.
10. The use of the Li-Ga-I-O and Na-Ga-I-O nonlinear optical crystal according to claim 4, wherein the Li-Ga-I-O and Na-Ga-I-O nonlinear optical crystal is used in nonlinear optical devices such as second harmonic generators, upper and lower frequency converters, optical parametric oscillators, laser frequency converters, laser communications, etc.
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| CN106283193A (en) * | 2015-05-27 | 2017-01-04 | 中国科学院新疆理化技术研究所 | Bromine gallium barium borate sodium and bromine gallium barium borate sodium nonlinear optical crystal and preparation method and purposes |
| CN110129876A (en) * | 2019-05-28 | 2019-08-16 | 天津理工大学 | Compound lead boron oxygen iodine and lead boron oxygen iodine nonlinear optical crystal and preparation method and purposes |
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| CN110129876A (en) * | 2019-05-28 | 2019-08-16 | 天津理工大学 | Compound lead boron oxygen iodine and lead boron oxygen iodine nonlinear optical crystal and preparation method and purposes |
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