CN115467023B - Compound lithium gallium iodic oxide and sodium gallium iodic oxide, lithium gallium iodic oxide and sodium gallium iodic oxide nonlinear optical crystal, preparation method and application thereof - Google Patents
Compound lithium gallium iodic oxide and sodium gallium iodic oxide, lithium gallium iodic oxide and sodium gallium iodic oxide nonlinear optical crystal, preparation method and application thereof Download PDFInfo
- Publication number
- CN115467023B CN115467023B CN202211252668.6A CN202211252668A CN115467023B CN 115467023 B CN115467023 B CN 115467023B CN 202211252668 A CN202211252668 A CN 202211252668A CN 115467023 B CN115467023 B CN 115467023B
- Authority
- CN
- China
- Prior art keywords
- gallium
- sodium
- lithium
- iodate
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 181
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 181
- 239000011734 sodium Substances 0.000 title claims abstract description 136
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 135
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 98
- 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 93
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000013078 crystal Substances 0.000 title claims abstract description 86
- 150000001875 compounds Chemical class 0.000 title claims abstract description 81
- 230000003287 optical effect Effects 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims abstract description 112
- 238000000034 method Methods 0.000 claims abstract description 21
- 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
- 239000000463 material Substances 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 47
- -1 polytetrafluoroethylene Polymers 0.000 claims description 34
- 238000001816 cooling Methods 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 30
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 21
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000227 grinding Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- 239000012071 phase Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 11
- 229910052740 iodine Inorganic materials 0.000 claims description 11
- 239000011630 iodine Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 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
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 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
- 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
- 238000004090 dissolution Methods 0.000 claims 1
- 238000011049 filling Methods 0.000 claims 1
- 230000005855 radiation Effects 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 description 19
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 12
- 229910000450 iodine oxide Inorganic materials 0.000 description 10
- AFSVSXMRDKPOEW-UHFFFAOYSA-N oxidoiodine(.) Chemical compound I[O] AFSVSXMRDKPOEW-UHFFFAOYSA-N 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- PRXLCSIMRQFQMX-UHFFFAOYSA-N [O].[I] Chemical compound [O].[I] PRXLCSIMRQFQMX-UHFFFAOYSA-N 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 8
- 239000010431 corundum Substances 0.000 description 8
- 238000002083 X-ray spectrum Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 150000002259 gallium compounds Chemical class 0.000 description 5
- 150000002497 iodine compounds Chemical class 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
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 3
- 230000001427 coherent effect Effects 0.000 description 2
- 238000010586 diagram Methods 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
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000013461 design Methods 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
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
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
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to a compound lithium gallium iodic oxide and sodium gallium iodic oxide, a lithium gallium iodic oxide and sodium gallium iodic oxide nonlinear optical crystal, a preparation method and application thereof, wherein chemical formulas of the compound and the crystal are AGa (IO) 3 ) 4 Wherein a=li, na, all belong to monoclinic system, space group P2 1 The unit cell parameters arec= 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 lithium gallium iodate and sodium gallium iodate are prepared by adopting a hydrothermal method and a solid-phase reaction method, the lithium gallium iodate and sodium gallium iodate nonlinear optical crystal grows by adopting the hydrothermal method, the solid-phase reaction method or the 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 a compound lithium gallium iodic oxide and sodium gallium iodic oxide and a lithium gallium iodic oxide and sodium gallium iodic oxide nonlinear optical crystal, wherein the molecular general formulas of the compound lithium gallium iodic oxide and sodium gallium iodic oxide and the lithium gallium iodic oxide and sodium gallium iodic oxide crystal are AGa (IO) 3 ) 4 Wherein a=li, na, a process for producing the crystal and a process for producing the crystalA nonlinear optical device is provided.
Background
Mid-far infrared coherent light with wavelengths between 3 and 14 μm is becoming increasingly important for its potential application in semiconductor lithography, laser micromachining and modern scientific instrumentation. For solid-state lasers, the acquisition of mid-far infrared coherent light is achieved by cascaded frequency conversion techniques of nonlinear optical crystals. However, for a suitable mid-far infrared nonlinear optical crystal, it must meet the following demanding structural and performance requirements, including i) a non-centrosymmetric structure; ii) large second order nonlinear optical coefficient (d) ij ) At least with d of KDP 36 Equivalent; iii) High transparency in the mid-far infrared region; iv) medium birefringence (Δn=0.03-0.1) to meet the phase matching conditions for medium far infrared second harmonic generation; v) easy preparation, non-toxicity, chemical stability and good mechanical properties. However, the contradiction of some of the above properties is that the large band gap material tends to exhibit smaller frequency multiplication response and birefringence, and far infrared nonlinear optical crystal still remains a great challenge in design and synthesis.
Metal iodate is a powerful candidate for mid-infrared NLO applications because of its broad transparency from the visible region to the far infrared (12.5 μm), wider band gap, and higher laser damage threshold are therefore widely studied. Due to I V Ion with stereochemically active lone pair electrons, IO 3 The unit is a good NLO active anionic group, has larger microscopic secondary NLO sensitivity, and arranges IO in a polar or non-centrosymmetric (NCS) crystal structure 3 The unit can produce a composite material with excellent Second Harmonic (SHG) properties, which is a candidate for the synthesis of NLO crystalline materials.
Disclosure of Invention
It is an object of the present invention to provide compounds lithium gallium iodate and sodium gallium iodate and methods of making the same.
The second object of the invention is to provide lithium gallium iodate and sodium gallium iodate nonlinear optical crystal and preparation method thereof.
It is a further object of the present invention to provide the use of lithium gallium iodate and sodium gallium iodate nonlinear optical crystals.
One of the objects of the present invention is achieved by:
the invention aims at providing compounds lithium gallium iodate and sodium gallium iodate, which are characterized in that the chemical formulas of the compounds are AGa (IO) 3 ) 4 Wherein a=li, na, molecular weights 776.26 and 792.31. The compounds lithium gallium iodate and sodium gallium iodate are prepared by adopting a hydrothermal method or a solid phase reaction method according to the following chemical reaction formula:
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 object of the invention is realized in that:
the invention aims at providing a lithium gallium iodic oxide and sodium gallium iodic oxide nonlinear optical crystal, which is characterized in that the chemical formula of the lithium gallium iodic oxide and sodium gallium iodic oxide nonlinear optical crystal is AGa (IO) 3 ) 4 Wherein a=li, na, has no symmetry center, belongs to monoclinic system, is a space group P2 1 The unit cell parameters arec= 10.502 (5) -11.335 (4), α=90°, β= 90.255 (17) ° -91.850 (14), γ=90°, z=2. The lithium gallium iodate and sodium gallium iodate nonlinear optical crystal are grown by a hydrothermal method or a solid phase reaction method or a solution method.
The hydrothermal method grows lithium gallium iodate and sodium gallium iodate nonlinear optical crystals, and molecular formulas of the lithium gallium iodate and the sodium gallium iodate nonlinear optical crystals are LiGa (IO) respectively 3 ) 4 And NaGa (IO) 3 ) 4 The specific operation is carried out according to the following steps:
a. adding an A=Li, na compound, gallium compound and iodine compound into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and adding 0.1-50mL of deionized water or 0.1-50g of mineralizer to fully and uniformly mix the materials to obtain a mixed solution, wherein the molar ratio of the A=Li, the Na compound, the gallium compound and the iodine compound is 0-2:0-2:3-5.
b. And c, screwing the cover of the polytetrafluoroethylene lining where the mixed solution is positioned 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 crystal to obtain the transparent lithium gallium iodate and sodium gallium iodate nonlinear optical crystal.
AGa (IO) is grown by the solid phase reaction method 3 ) 4 Wherein a=li, na nonlinear optical crystal, the specific operation is performed as follows:
uniformly mixing single-phase polycrystalline powder of lithium gallium ioxide and sodium gallium ioxide with a fluxing agent, heating to 150-500 ℃, keeping the temperature for a long time, and cooling to room temperature, wherein the molar ratio of the single-phase polycrystalline powder of lithium gallium ioxide and sodium gallium ioxide to the fluxing agent is 1:0-10;
or directly heating a mixture containing A=Li, na compound, gallium compound and iodine compound or a mixture containing A=Li, na compound, gallium compound and iodine compound and fluxing agent to 150-500 ℃ for a long time, and cooling to room temperature, wherein the molar ratio of the A=Li, na compound, gallium compound and iodine compound to the fluxing agent is 0-2:0-2:3-5:1-10;
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, diiodide and periodic acid.
The solution method for growing lithium gallium iodate and sodium gallium iodate nonlinear optical crystal comprises the following steps:
a=li, na, gallium and iodine containing compounds were added to a beaker and deionized water 0.1-400mL was added and the solution was stirred until clear. And then placing the beaker on a heating table, and heating to 25-400 ℃ for a period of time to obtain the lithium gallium iodate and sodium gallium iodate nonlinear optical crystal. To further grow it, the seed crystal of the series of crystals is suspended in solution with a fine platinum wire. To reduce the evaporation of water, the beaker was covered with a polyethylene plate and perforated with holes of a size of several tens of millimeters. After a period of time, the lithium gallium iodate and sodium gallium iodate nonlinear optical crystals are removed from the solution.
The third object of the present invention is achieved by:
the lithium gallium ioxix and sodium gallium ioxix nonlinear optical crystal is suitable for a middle-far infrared band laser frequency conversion device, an infrared communication device and an infrared laser guidance device, and is used for preparing nonlinear optical devices such as a second harmonic generator, an upper or lower frequency converter or an optical parametric oscillator.
Drawings
FIG. 1 is a theoretical X-ray spectrum of a lithium gallium iodate crystal of the present invention
FIG. 2 is a theoretical X-ray spectrum of a crystal of sodium gallium iodate prepared in accordance with the present invention
FIG. 3 shows AGa (IO) 3 ) 4 A = Li, na crystal structure diagram;
fig. 4 is a schematic diagram of nonlinear optical effects of lithium gallium iodate and sodium gallium iodate crystals when applied 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, 6 is a KTP crystal, 7 is an OPO output mirror and a light total reflection mirror of 1064nm wavelength, 8 is a light reflection mirror of 2.1 μm wavelength, 9 is an AGa (IO) after crystal post-treatment and optical processing 3 ) 4 Where a=li, na single crystal, 10 is the generated outgoing laser beam.
Detailed Description
The invention is described in detail below with reference to the drawings and examples of implementation, but is not limited to the described embodiments. Any modifications and variations made on the basis of the present invention are within the scope of the present invention.
Example 1
According to the reaction formula: a is that 2 CO 3 (A＝Li，Na)+Ga 2 O 3 +8HIO 3 →2AGa(IO 3 ) 4 (A＝Li，Na)+4H 2 O↑+CO 2 ∈, synthesis of AGa (IO) 3 ) 4 (a=li, na) compound:
a. will A 2 CO 3 (A＝Li，Na)、Ga 2 O 3 、HIO 3 Directly weighing raw materials according to a molar ratio of 1:1:8, adding the raw materials into a polytetrafluoroethylene lining of a high-pressure reaction kettle with a volume of 150mL, adding 30mL of deionized water and 10g of diiodide, and fully and uniformly mixing the raw materials to obtain a mixed solution;
b. screwing the polytetrafluoroethylene lining cover where the mixed solution is located in the step a, then putting the polytetrafluoroethylene lining cover into a clean 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 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 the compounds lithium gallium iodate and sodium gallium iodate, wherein the obtained product is transparent crystals.
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. AOH (a=li, na), ga 2 O 3 、HIO 3 Directly weighing raw materials according to a molar ratio of 2:1:8, adding the raw materials into a polytetrafluoroethylene lining of a high-pressure reaction kettle with a volume of 23mL, and adding 1mL of deionized water to fully and uniformly mix the raw materials to obtain a mixed solution;
b. screwing the polytetrafluoroethylene lining cover where the mixed solution is located in the step a, then putting the polytetrafluoroethylene lining cover into a clean 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 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. and opening the high-pressure reaction kettle, and filtering the solution containing the crystals to obtain the compounds lithium gallium iodate and sodium gallium iodate, wherein the obtained product is 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 +. 3 ) 4 (a=li, na) compound:
a. AF (a=li, na), ga 2 O 3 、HIO 3 Directly weighing raw materials according to a molar ratio of 1:1:4, adding the raw materials into a polytetrafluoroethylene lining of a high-pressure reaction kettle with a volume of 100mL, adding 25mL of deionized water and 5g of periodic acid, and fully and uniformly mixing the raw materials to obtain a mixed solution;
b. screwing the polytetrafluoroethylene lining cover where the mixed solution is located in the step a, then putting the polytetrafluoroethylene lining cover into a clean 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 the compounds lithium gallium iodate and sodium gallium iodate, wherein the obtained product is transparent crystals.
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 ≡, synthetic AGa (IO) 3 ) 4 (a=li, na) compound:
a. AF (a=li, na), ga 2 O 3 、I 2 O 5 Directly weighing raw materials according to a molar ratio of 5:1:2, adding the raw materials into a polytetrafluoroethylene lining of a high-pressure reaction kettle with a volume of 150mL, and adding 50mL of deionized water to fully and uniformly mix the raw materials to obtain a mixed solution;
b. screwing the polytetrafluoroethylene lining cover where the mixed solution is located in the step a, then putting the polytetrafluoroethylene lining cover into a clean 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 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 the compounds lithium gallium iodate and sodium gallium iodate, wherein the obtained product is 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. AF (a=li, na), ga 2 O 3 、H 5 IO 6 Directly weighing raw materials according to a molar ratio of 2:1:8, adding the raw materials into a polytetrafluoroethylene lining of a high-pressure reaction kettle with a volume of 150mL, and adding 50mL of deionized water to fully and uniformly mix the raw materials to obtain a mixed solution;
b. screwing the polytetrafluoroethylene lining cover where the mixed solution is located in the step a, then putting the polytetrafluoroethylene lining cover into a clean 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 300 ℃ 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 the compounds lithium gallium iodate and sodium gallium iodate, wherein the obtained product is transparent crystals.
Example 6
According to reaction type 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 ∈, synthesis of AGa (IO) 3 ) 4 (a=li, na) compound:
will A 2 CO 3 (A＝Li，Na)、Ga 2 O 3 、HIO 3 Weighing and putting into a mortar according to the molar ratio of 1:1:8Mixing, fine grinding, placing into an open corundum crucible with phi of 100mm×100mm, slowly heating to 100deg.C, keeping constant temperature for 24 hr, cooling to room temperature, taking out, grinding for the second time, placing into a muffle, keeping constant temperature for 24 hr, cooling to room temperature, taking out, grinding for the third time, placing into a muffle, keeping constant temperature for 24 hr at 150deg.C, taking out, grinding to obtain single-phase polycrystalline powder of lithium gallium iodine oxide and sodium gallium iodine oxide, performing X-ray analysis, and collecting X-ray spectrogram and single-phase polycrystalline powder of lithium gallium iodine oxide and sodium gallium iodine oxide AGa (IO) 3 ) 4 The X-ray spectra obtained for the (a=li, na) single crystal structure are consistent;
the obtained compounds lithium gallium iodate and sodium gallium iodate, AGa (IO 3 ) 4 (a=li, na), loading single-phase polycrystalline powder into an open corundum crucible with phi of 100mm×100mm, keeping the temperature at 150 ℃ for 120 hours, and cooling to room temperature at a cooling rate of 2 ℃/h to obtain lithium gallium iodate and sodium gallium iodate 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 ≡, synthetic AGa (IO) 3 ) 4 (a=li, na) compound:
AOH (a=li, na), ga 2 O 3 、HIO 3 Weighing and placing into a mortar according to a molar ratio of 2:1:8, mixing and grinding finely, then placing into an open corundum crucible with phi of 100mm multiplied by 100mm, placing into a muffle furnace, slowly heating to 350 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, grinding for the second time, placing into the muffle furnace, heating to 400 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, grinding for the third time, placing into the muffle furnace, keeping the temperature for 24 hours at 500 ℃, taking out, grinding to obtain single-phase polycrystalline powder of the compound lithium gallium iodine oxygen and sodium gallium iodine oxygen, and carrying out X-ray analysis on the product to obtain an X-ray spectrogram and the compound lithium gallium iodine oxygen and sodium gallium iodine oxygen, AGa (IO) 3 ) 4 (a=li, na), the X-ray spectra obtained for the single crystal structure are consistent;
the obtained compounds of lithium gallium iodate and sodium galliumIohexon, AGa (IO) 3 ) 4 (a=li, na), loading single-phase polycrystalline powder into an open corundum crucible with phi of 100mm x 100mm, keeping the temperature at 500 ℃ for 120 hours, and cooling to room temperature at a cooling rate of 2 ℃/h to obtain lithium gallium iodate and sodium gallium iodate 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 ∈, synthesis of AGa (IO) 3 ) 4 (a=li, na) compound:
AF (a=li, na), ga 2 O 3 、HIO 3 Weighing and placing into a mortar according to a molar ratio of 2:1:8, mixing and grinding finely, then placing into an open corundum crucible with phi of 100mm multiplied by 100mm, placing into a muffle furnace, slowly heating to 250 ℃, keeping the temperature constant for 24 hours, cooling to room temperature, taking out, grinding for the second time, placing into the muffle furnace, heating to 300 ℃, keeping the temperature constant for 24 hours, cooling to room temperature, taking out, grinding for the third time, placing into the muffle furnace, keeping the temperature constant for 24 hours at 400 ℃, taking out, grinding to obtain single-phase polycrystalline powder of the compound lithium gallium iodine oxygen and sodium gallium iodine oxygen, carrying out X-ray analysis on the product, and obtaining an X-ray spectrogram, the compound lithium gallium iodine oxygen and sodium gallium iodine oxygen, AGa (IO) 3 ) 4 (a=li, na), the X-ray spectra obtained for the single crystal structure are consistent;
the obtained compounds lithium gallium iodate and sodium gallium iodate, AGa (IO 3 ) 4 (a=li, na), loading single-phase polycrystalline powder into an open corundum crucible with phi of 100mm x 100mm, keeping the temperature at 450 ℃ for 120 hours, and cooling the powder to room temperature at a cooling rate of 2 ℃/h to obtain lithium gallium iodate and sodium gallium iodate 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 ∈, AGa (IO 3 ) 4 (a=li, na) compound:
ACl (a=li, na), ga 2 O 3 、HIO 3 Weighing and putting into a mortar according to a molar ratio of 2:1:8Mixing, fine grinding, placing into open corundum crucible with phi of 100mm×100mm, placing into muffle furnace, slowly heating to 200deg.C, keeping constant temperature for 24 hr, cooling to room temperature, taking out, grinding for the second time, placing into muffle furnace, keeping constant temperature for 24 hr, cooling to room temperature, taking out, grinding for the third time, placing into muffle furnace, keeping constant temperature for 24 hr at 300deg.C, taking out single-phase polycrystalline powder of lithium gallium iodine oxide and sodium gallium iodine oxide, grinding to obtain single-phase polycrystalline powder of lithium gallium iodine oxide and sodium gallium iodine oxide, performing X-ray analysis on the product, and collecting X-ray spectrogram and single-phase polycrystalline powder of lithium gallium iodine oxide and sodium gallium iodine oxide, AGa (IO 3 ) 4 (a=li, na), the X-ray spectra obtained for the single crystal structure are consistent;
the obtained compounds lithium gallium iodate and sodium gallium iodate, AGa (IO 3 ) 4 (a=li, na), loading single-phase polycrystalline powder into an open corundum crucible with phi of 100mm×100mm, keeping the temperature at 300 ℃ for 120 hours, and cooling to room temperature at a cooling rate of 2 ℃/h to obtain lithium gallium iodate and sodium gallium iodate crystals;
example 10
According to the reaction formula: a is that 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:
will A 2 CO 3 (A＝Li，Na)、GaCl 3 、HIO 3 The raw materials were weighed directly in a molar ratio of 1:2:8 and added to a 1000mL beaker, followed by 400mL deionized water, and the solution was stirred until clear. And then placing the beaker on a heating table, and heating to 400 ℃ for 7 days to obtain the lithium gallium iodate and sodium gallium iodate nonlinear optical crystal. To further grow it, the seed crystal of the series of crystals is suspended in solution with a fine platinum wire. To reduce the evaporation of water, the beaker was covered with a polyethylene plate and perforated with holes of a size of several tens of millimeters. After 3 weeks, larger lithium gallium iodate and sodium gallium iodate 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 ∈, AGa (IO 3 ) 4 (a=li, na) compound:
AOH (a=li, na), gaCl 3 、HIO 3 The raw materials were directly weighed in a molar ratio of 1:1:4 and added to a beaker with a volume of 100mL, followed by addition of deionized water 20mL, and the solution was stirred until clear. And then placing the beaker on a heating table, and heating to 300 ℃ for 7 days to obtain the lithium gallium iodate and sodium gallium iodate nonlinear optical crystal. To further grow it, the seed crystal of the series of crystals is suspended in solution with a fine platinum wire. To reduce the evaporation of water, the beaker was covered with a polyethylene plate and perforated with holes of a size of several tens of millimeters. After 5 weeks, larger lithium gallium iodate and sodium gallium iodate 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 +. 3 ) 4 (a=li, na) compound:
AF (a=li, na), gaCl 3 、HIO 3 The raw materials were directly weighed in a molar ratio of 1:1:4 and added to a 50mL beaker, followed by 10mL of deionized water, and the solution was stirred until clear. And then placing the beaker on a heating table, and heating to 150 ℃ for 12 days to obtain the lithium gallium iodate and sodium gallium iodate nonlinear optical crystal. To further grow it, the seed crystal of the series of crystals is suspended in solution with a fine platinum wire. To reduce the evaporation of water, the beaker was covered with a polyethylene plate and perforated with holes of a size of several tens of millimeters. After 4 weeks, larger lithium gallium iodate and sodium gallium iodate 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 ∈ to synthesize AGa (IO) 3 ) 4 (a=li, na) compound:
ACl (a=li, na), gaCl 3 、HIO 3 The raw materials were directly weighed in a molar ratio of 1:1:4 and added to a beaker with a volume of 10mL, and deionized water 2mL was added, and the solution was stirred until clear. And then placing the beaker on a heating table, and heating to 25 ℃ for 9 days to obtain the lithium gallium iodate and sodium gallium iodate nonlinear optical crystal. To further grow it, the seed crystal of the series of crystals is suspended in solution with a fine platinum wire. To reduce the evaporation of water, the beaker was covered with a polyethylene plate and perforated with holes of a size of several tens of millimeters. After 5 weeks, larger lithium gallium iodate and sodium gallium iodate nonlinear optical crystals were removed from the solution.
Example 14
Processing a frequency doubling device with the size of 5mm multiplied by 6mm according to the matching direction of any lithium gallium ioxix and sodium gallium ioxix crystal obtained in the examples 1-13, placing the frequency doubling device at the 9 position in the device shown in fig. 4 after processing, and adjusting Q Nd at room temperature; YAG laser is externally added with OPO as an input light source, the incident wavelength is 2100nm, and the output of frequency multiplication light of 1050nm is received through a photomultiplier tube.
Claims (8)
1. The compounds lithium gallium iodic oxide and sodium gallium iodic oxide are characterized in that the molecular general formula of the compounds lithium gallium iodic oxide and sodium gallium iodic oxide is AGa (IO) 3 ) 4 Wherein a=li or Na, and the formulae are respectively LiGa (IO 3 ) 4 And NaGa (IO) 3 ) 4 The molecular weights were 776.26 and 792.31, respectively.
2. A process for preparing the compounds lithium gallium iodate and sodium gallium iodate according to claim 1, characterized in that it is prepared by hydrothermal method or solid phase reaction method.
3. The method for preparing the compounds lithium gallium iodate and sodium gallium iodate according to claim 2, characterized in that:
the specific operation of preparing the compounds lithium gallium iodate and sodium gallium iodate by the hydrothermal method is as follows: adding a lithium-containing or sodium-containing 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, fully and uniformly mixing to obtain a mixed solution, wherein the molar ratio of the lithium-containing or sodium-containing compound to the gallium-containing compound to the iodine-containing compound to the mineralizer is 0-2:0-2:3-5:0-10, filling the polytetrafluoroethylene lining into the high-pressure kettle, heating the high-pressure kettle in an incubator, cooling to room temperature, and filtering a solution containing powder to obtain the compounds lithium gallium iodate and sodium gallium iodate;
the specific operation of preparing the compounds lithium gallium iodate and sodium gallium iodate by the solid phase reaction method is as follows: uniformly mixing a lithium-containing compound or sodium-containing compound, a gallium-containing compound and an iodine-containing compound, grinding, putting into a muffle furnace, and calcining for multiple times during grinding and calcining to obtain single-phase polycrystalline powder of the lithium gallium iodate and sodium gallium iodate, wherein the molar ratio of the lithium-containing compound or sodium-containing compound to the gallium-containing compound to the iodine-containing compound is 0-2:0-2:3-5;
wherein the number of moles of the lithium-or sodium-containing compound is calculated as the number of moles of the lithium element contained therein; the mole number of the gallium-containing compound is calculated by the mole number of the gallium element contained therein; the mole number of the iodine-containing compound is calculated by the mole number of iodine element contained therein;
the lithium or sodium-containing compound comprises at least one of lithium hydroxide or sodium hydroxide, lithium oxide or sodium oxide and alkali metal salt, wherein the alkali metal salt comprises 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 lithium gallium iodic oxide and sodium gallium iodic oxide nonlinear optical crystal is characterized in that the chemical formulas of the two crystals are AGa (IO) 3 ) 4 Wherein a=li or Na, both belong to monoclinic system, space group P2 1 The unit cell parameters are a= 9.110 (4) -9.450 (3) a, b= 5.124 (3) -5.465 (19) a, c=10.502(5)-11.335(4), α =90°, β = 90.255(17)°-91.850(14), γ= 90°，Z=2。
5. A method for preparing the lithium gallium iodate and sodium gallium iodate nonlinear optical crystal according to claim 4, wherein the lithium gallium iodate and sodium gallium iodate nonlinear optical crystal is grown by a hydrothermal method and a solution method.
6. The method for preparing lithium gallium iodate and sodium gallium iodate nonlinear optical crystal according to claim 5, wherein the method comprises the following steps:
the specific operation of growing the lithium gallium iodate and sodium gallium iodate nonlinear optical crystal by the hydrothermal method is as follows: adding the compound lithium gallium iodate and sodium gallium iodate obtained in claim 1 or the mixture of the compound lithium gallium iodate and sodium gallium iodate obtained in claim 1 and a mineralizer, or directly adding the lithium-containing or sodium-containing compound, the gallium-containing compound and the iodine-containing compound or the mixture of the lithium-containing or sodium-containing compound, the gallium-containing compound and the iodine-containing compound and the mineralizer into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and then adding deionized water to fully and uniformly mix the materials to obtain a mixed solution; putting a polytetrafluoroethylene lining into an autoclave, heating the autoclave in an incubator, cooling to room temperature, and filtering a solution containing crystals to obtain transparent lithium gallium iodate or sodium gallium iodate nonlinear optical crystals;
the specific operation of the solution method for growing lithium gallium iodate and sodium gallium iodate nonlinear optical crystal is as follows: adding the lithium gallium iodate and sodium gallium iodate obtained in the method in a beaker, adding deionized water for dissolution, stirring the solution until the solution is clear, then placing the beaker in air, and evaporating the solution to grow the lithium gallium iodate or sodium gallium iodate nonlinear optical crystal.
7. The preparation method according to claim 6, wherein the molar ratio of the single-phase polycrystalline powder of the compounds lithium gallium iodate and sodium gallium iodate to the mineralizer is 1:0-10; or wherein the molar ratio of lithium-or sodium-containing compounds, gallium-containing compounds and iodine-containing compounds to mineralizer is from 0 to 2:0 to 2:3 to 5:0 to 10; 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, diiodide pentoxide, periodic acid, iodic acid, gallium oxide and gallium chloride.
8. A nonlinear optical device employing the lithium gallium iodate and sodium gallium iodate nonlinear optical crystals of claim 4, comprising means for passing at least one beam of incident electromagnetic radiation through at least one nonlinear optical crystal to produce at least one beam of output radiation having a frequency different from the incident electromagnetic radiation, wherein: wherein the nonlinear optical crystal is lithium gallium iodate and sodium gallium iodate nonlinear optical crystal, AGa (IO) 3 ) 4 Wherein a=li or Na.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211252668.6A CN115467023B (en) | 2022-10-13 | 2022-10-13 | Compound lithium gallium iodic oxide and sodium gallium iodic oxide, lithium gallium iodic oxide and sodium gallium iodic oxide nonlinear optical crystal, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211252668.6A CN115467023B (en) | 2022-10-13 | 2022-10-13 | Compound lithium gallium iodic oxide and sodium gallium iodic oxide, lithium gallium iodic oxide and sodium gallium iodic oxide nonlinear optical crystal, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115467023A CN115467023A (en) | 2022-12-13 |
| CN115467023B true CN115467023B (en) | 2023-11-07 |
Family
ID=84337364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211252668.6A Active CN115467023B (en) | 2022-10-13 | 2022-10-13 | Compound lithium gallium iodic oxide and sodium gallium iodic oxide, lithium gallium iodic oxide and sodium gallium iodic oxide nonlinear optical crystal, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115467023B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2022
- 2022-10-13 CN CN202211252668.6A patent/CN115467023B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| Hongwei Yu et al..Syntheses, characterization and calculations of LimAnM6O15 (A=Rb, Cs * |
| LiGaF2(IO3)2: A mixed-metal gallium iodate-fluoride with large birefringence and wide band gap;Jin Chen et al.;《SCIENCE CHINA Materials》;第2卷(第64期);400-407 * |
| M=Si, Ge ; m+n=6).《SCIENCE CHINA Materials》.2020,第9卷(第63期),1769-1778. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115467023A (en) | 2022-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101798707B (en) | BaMgBO3F non-linear optical crystal, preparation method and applications thereof | |
| CN101799609B (en) | BaMgBO3F non-linear optical crystal, preparation method and applications thereof | |
| CN101545138A (en) | Non-linear optical crystal-sodium beryllate borate, growth method and application thereof | |
| WO2016086425A1 (en) | Nonlinear optical crystal material, method for preparation thereof, and application thereof | |
| CN103205811B (en) | Large size chlorine barium fluoborate non-linear optic crystal and its production and use | |
| CN102828245B (en) | NaCaBe2B2O6 nonlinear optical crystal, its growth method and application thereof | |
| CN102828246B (en) | NaSr3Be3B3O9F4 nonlinear optical crystal, its growth method and application thereof | |
| CN110396721A (en) | Fluorine boron aluminic acid cesium compound, fluorine boron aluminic acid caesium nonlinear optical crystal and its preparation method and application | |
| CN115467023B (en) | Compound lithium gallium iodic oxide and sodium gallium iodic oxide, lithium gallium iodic oxide and sodium gallium iodic oxide nonlinear optical crystal, preparation method and application thereof | |
| CN110129876B (en) | Compound lead boron oxygen iodine and lead boron oxygen iodine nonlinear optical crystal, preparation method and application | |
| CN102352533A (en) | Novel nonlinear optical crystal beryllium-sodium-cesium borate | |
| CN105274621B (en) | A kind of molybdophosphate fluorine potassium compound, its nonlinear optical crystal and its production and use | |
| CN104213193B (en) | Phosphomolybdate compound, phosphomolybdate nonlinear optical crystals, and preparation method and applications of phosphomolybdate nonlinear optical crystals | |
| CN103834995B (en) | Boron beryllate compound, boron beryllate nonlinear optical crystal and preparation method and purposes | |
| CN113846381B (en) | Compound barium yttrium borate and barium yttrium borate nonlinear optical crystal, and preparation method and application thereof | |
| CN102260912A (en) | Novel nonlinear optical crystal low-temperature phase kalium beryllium borate | |
| CN102260913B (en) | Nonlinear optical crystal rubidium beryllium borate | |
| CN102260911A (en) | Novel nonlinear optical crystal medium temperature-phase potassium beryllium borate | |
| CN109160526B (en) | Li8NaRb3(SO4)6·2H2O compound, nonlinear optical crystal, and preparation method and application thereof | |
| CN101984152B (en) | Nonlinear optical crystal of dimalic acid ammonium borate monohydrate compound and growing method and application thereof | |
| CN109208076A (en) | Rb4Cd2I8·H2O compound, nonlinear optical crystal and its preparation method and purposes | |
| CN104562204A (en) | Cesium tungsten-tellurite crystal as well as flux growth method and application thereof | |
| CN115404550B (en) | Gallium selenium oxygen fluorine hydrogen compound, preparation method and application of gallium selenium oxygen fluorine hydrogen nonlinear optical crystal | |
| US20240067876A1 (en) | Series of Alkali Metal Borophosphates Compounds, and Alkali Metal Borophosphates Nonlinear Optical Crystals as well as Preparation Method and Application thereof | |
| CN115418722A (en) | Alkaline earth metal fluorine-containing iodate compound, nonlinear optical crystal thereof, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |