CN113668055A - Compound potassium molybdenum phosphate and potassium molybdenum phosphate nonlinear optical crystal, and preparation method and application thereof - Google Patents
Compound potassium molybdenum phosphate and potassium molybdenum phosphate nonlinear optical crystal, and preparation method and application thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 151
- ZNFVDPDMSKPTGV-UHFFFAOYSA-K potassium molybdenum(4+) phosphate Chemical compound P(=O)([O-])([O-])[O-].[K+].[Mo+4] ZNFVDPDMSKPTGV-UHFFFAOYSA-K 0.000 title claims abstract description 47
- 230000003287 optical effect Effects 0.000 title claims abstract description 39
- -1 Compound potassium molybdenum phosphate Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 111
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- 238000001816 cooling Methods 0.000 claims description 39
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 33
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 32
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 32
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 25
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 25
- 239000011591 potassium Substances 0.000 claims description 25
- 229910052700 potassium Inorganic materials 0.000 claims description 25
- 229910052750 molybdenum Inorganic materials 0.000 claims description 23
- 239000011733 molybdenum Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 22
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 20
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 19
- 239000001103 potassium chloride Substances 0.000 claims description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims description 17
- 239000011574 phosphorus Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 14
- 235000011164 potassium chloride Nutrition 0.000 claims description 14
- 150000003017 phosphorus Chemical class 0.000 claims description 13
- GDXTWKJNMJAERW-UHFFFAOYSA-J molybdenum(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mo+4] GDXTWKJNMJAERW-UHFFFAOYSA-J 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 11
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 11
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 11
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 11
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 11
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 10
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 10
- CZDSWLXAULJYPZ-UHFFFAOYSA-J molybdenum(4+);dicarbonate Chemical compound [Mo+4].[O-]C([O-])=O.[O-]C([O-])=O CZDSWLXAULJYPZ-UHFFFAOYSA-J 0.000 claims description 10
- YJEJUIVHAMABCA-UHFFFAOYSA-J molybdenum(4+);oxalate Chemical compound [Mo+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O YJEJUIVHAMABCA-UHFFFAOYSA-J 0.000 claims description 10
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 10
- 239000011736 potassium bicarbonate Substances 0.000 claims description 10
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 10
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 10
- 235000011181 potassium carbonates Nutrition 0.000 claims description 10
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 10
- 235000010333 potassium nitrate Nutrition 0.000 claims description 10
- 239000004323 potassium nitrate Substances 0.000 claims description 10
- 235000011151 potassium sulphates Nutrition 0.000 claims description 10
- YPFBRNLUIFQCQL-UHFFFAOYSA-K tribromomolybdenum Chemical compound Br[Mo](Br)Br YPFBRNLUIFQCQL-UHFFFAOYSA-K 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 5
- 150000002751 molybdenum Chemical class 0.000 claims description 5
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 5
- 229910017677 NH4H2 Inorganic materials 0.000 claims description 4
- 230000004907 flux Effects 0.000 claims description 3
- QBHSCXQMHIQUMU-UHFFFAOYSA-N OC(C(O)=O)=O.OC(C(O)=O)=O.OC(C(O)=O)=O.P.P Chemical compound OC(C(O)=O)=O.OC(C(O)=O)=O.OC(C(O)=O)=O.P.P QBHSCXQMHIQUMU-UHFFFAOYSA-N 0.000 claims description 2
- ZCEAYPNEFSJYFM-UHFFFAOYSA-N OC(O)=O.OC(O)=O.OC(O)=O.P.P Chemical compound OC(O)=O.OC(O)=O.OC(O)=O.P.P ZCEAYPNEFSJYFM-UHFFFAOYSA-N 0.000 claims description 2
- LMFWXTZEFKLNSB-UHFFFAOYSA-N OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.P.P Chemical compound OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.P.P LMFWXTZEFKLNSB-UHFFFAOYSA-N 0.000 claims description 2
- HYWKVFVQRGEFCH-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[PH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[PH6+3] HYWKVFVQRGEFCH-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical compound BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 claims description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims 2
- 229910000464 lead oxide Inorganic materials 0.000 claims 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims 1
- 229910000160 potassium phosphate Inorganic materials 0.000 claims 1
- 235000011009 potassium phosphates Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 229910003069 TeO2 Inorganic materials 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 16
- 235000011118 potassium hydroxide Nutrition 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 8
- 239000000155 melt Substances 0.000 description 7
- 229910015255 MoF6 Inorganic materials 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 239000012856 weighed raw material Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- RLCOZMCCEKDUPY-UHFFFAOYSA-H molybdenum hexafluoride Chemical compound F[Mo](F)(F)(F)(F)F RLCOZMCCEKDUPY-UHFFFAOYSA-H 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VYKYLQRTMKIQFY-UHFFFAOYSA-N [Mo].[K] Chemical compound [Mo].[K] VYKYLQRTMKIQFY-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/14—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
-
- 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
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/3551—Crystals
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Abstract
Compound potassium molybdenum phosphate and potassium molybdenum phosphate nonlinear optical crystal, preparation method and application thereof, wherein chemical formulas of the compound potassium molybdenum phosphate and the compound potassium molybdenum phosphate nonlinear optical crystal are K4Mo5P2O22The crystal belongs to the orthorhombic system, space group C2221Cell parameter of
Molecular weight of 262.51, and its powder frequency doubling effect is about 1 times KDP (KH)2PO4). The compound of the molybdenum potassium phosphate is synthesized by a solid-phase reaction method, the molybdenum potassium phosphate nonlinear optical crystal grows by a high-temperature melt method or a Czochralski method, the molybdenum potassium phosphate nonlinear optical crystal has high mechanical hardness, is easy to cut, polish, process and store, and is widely applied to the preparation of nonlinear optical devices such as a frequency doubling generator, an upper frequency converter, a lower frequency converter or an optical parametric oscillator.
Description
Technical Field
The invention relates to a compound of formula K4Mo5P2O22The compound of (1) potassium molybdenum phosphate, a potassium molybdenum phosphate nonlinear optical crystal, a preparation method of the crystal and a nonlinear optical device manufactured by using the crystal.
Background
The exploration of a novel nonlinear optical crystal with large frequency coefficient, high conversion efficiency, good chemical stability, wide transmission waveband and large optical damage threshold value is always a hot topic in the field of laser frequency conversion. The main nonlinear optical materials at present are: beta-BaB2O4(BBO) Crystal, KB3O5(LBO) crystal, CsB3O5(CBO) crystal, CsKB6O10(CLBO) Crystal and KBe2BO3F2(KBBF) crystal. Although the crystal growth techniques for these materials are becoming more sophisticated, there are still significant disadvantages: such as easy deliquescence of crystal, long growth period, serious lamellar growth habit, high price and the like. Therefore, finding new nonlinear optical crystal materials remains a very important and difficult task. In order to make up for the above shortcomings of nonlinear optical crystals, scientists in various countries still pay great attention to the exploration and research of various novel nonlinear optical crystals, not only pay attention to the optical properties and mechanical properties of the crystals, but also pay more and more attention to the preparation characteristics of the crystals.
Phosphate as a fluorescent matrix material is also one of the hot spots of research. From the visible to the ultraviolet rangeDue to their excellent luminescence properties and broad excitation bands, phosphate based materials have application value in color plasma flat panel displays and white light emitting diodes. The rare earth ion activated phosphate fluorescent material is BiPO4、Na3GdP2O8、Ba3LaNa(PO4)3F、Ca9Y(PO4)7、KSrPO4And the like, and the alkali metal cation (K) is introduced into the phosphate, has no electronic transition of d-d, and is a desirable choice for transmission in the ultraviolet region. Therefore, the synthesis of alkali metal phosphate is an effective means for designing the ultraviolet nonlinear optical material with large frequency doubling effect.
Disclosure of Invention
The invention aims to provide a compound of potassium molybdenum phosphate and a potassium molybdenum phosphate nonlinear optical crystal, wherein the chemical formulas of the potassium molybdenum phosphate and the potassium molybdenum phosphate are both K4Mo5P2O22；
The invention also aims to provide a preparation method for synthesizing the compound of the potassium molybdenum phosphate by adopting a solid-phase reaction method and growing the potassium molybdenum phosphate nonlinear optical crystal by adopting a high-temperature melt method or a pulling method;
it is a further object of the present invention to provide the use of the potassium molybdenum phosphate nonlinear optical device for the preparation of a frequency doubling generator, an upper or lower frequency converter or an optical parametric oscillator.
The technical scheme of the invention is as follows:
the compound of potassium molybdenum phosphate provided by the invention has a chemical formula of K4Mo5P2O22(ii) a The preparation process comprises the following steps: uniformly mixing raw materials of a potassium-containing compound, a molybdenum-containing compound and a phosphorus-containing compound, grinding, putting into a muffle furnace, presintering to remove moisture and gas in the raw materials, cooling to room temperature, taking out, grinding, putting into the muffle furnace, and calcining to obtain a compound, namely, potassium molybdenum phosphate;
the potassium-containing compound comprises at least one of potassium hydroxide, potassium oxide and potassium salt; the potassium salt comprises at least one of potassium chloride, potassium bromide, potassium nitrate, potassium oxalate, potassium carbonate, potassium bicarbonate and potassium sulfate;
the molybdenum-containing compound comprises at least one of molybdenum oxide, molybdenum hydroxide and molybdenum salt; the molybdenum salt comprises at least one of molybdenum chloride, molybdenum bromide, molybdenum nitrate, molybdenum oxalate, molybdenum carbonate and molybdenum sulfate;
the phosphorus-containing compound is phosphorus pentoxide, molybdenum hydroxide and a phosphorus salt; the phosphorus salt comprises at least one of phosphorus chloride, phosphorus bromide, phosphorus nitrate, phosphorus oxalate, phosphorus carbonate, ammonium dihydrogen phosphate and phosphorus sulfate;
the molybdenum potassium phosphate compound can be prepared according to the following chemical reaction formula by adopting a solid-phase reaction method:
1)2K2CO3+5MoO3+P2O5→K4Mo5P2O22+2CO2↑
2)KNO3+5MoO3+P2O5→K4Mo5P2O22+4NO2↑+2O2↑
3)4KOH+5MoO3+P2O5→2K4Mo5P2O22+2H2O↑
4)2K2SO4+5MoO3+P2O5→K4Mo5P2O22+2SO2↑+O2↑
5)2K2CO3+5MoO3+2NH4H2PO4→K4Mo5P2O22+2NH3↑+2CO2↑+3H2O↑
6)4KNO3+5MoO3+2NH4H2PO4→K4Mo5P2O22+4NO2↑+2NH3↑3H2O↑+O2↑
7)2K2C2O4+5MoO3+P2O5→K4Mo5P2O22+2CO↑+2CO2↑
8)2K2O+5Mo(CO3)3+P2O5→K4Mo5P2O22+15CO2↑
9)4KHCO3+5Mo(CO3)3+P2O5→K4Mo5P2O22+19CO2↑+2H2O↑
10)4KNO3+5Mo(NO3)6+P2O5→K4Mo5P2O22+14NO2↑+27O2↑+3NO↑
11)4K2CO3+10Mo(NO3)6+2P2O5→2K4Mo5P2O22+4CO↑+60NO2↑+17O2↑
12)8KOH+10Mo(NO3)6+2P2O5→2K4Mo5P2O22+60NO2↑+4H2O↑+15O2↑
13)4K2SO4+10Mo(NO3)6+2P2O5→2K4Mo5P2O22+60NO2↑+21O2↑
14)8KCl+10Mo(NO3)6+2P2O5→2K4Mo5P2O22+60NO2↑+4Cl2↑+13O2
the invention provides a potassium molybdenum phosphate nonlinear optical crystal which is characterized in that the chemical formula of the crystal is K4Mo5P2O22Molecular weight 262.51, not having a center of symmetry, belonging to orthorhombic system, space group C2221Cell parameter of
Molecular weight, its powder frequency doubling effect is about 1 times KDP (KH)2PO4). The invention provides potassium molybdenum phosphateThe preparation method of the nonlinear optical crystal adopts a high-temperature melt method or a Czochralski method to grow the molybdenum potassium phosphate nonlinear optical crystal, and comprises the following specific operations:
a. uniformly mixing the compound molybdenum potassium phosphate single-phase polycrystalline powder with a fluxing agent, heating the mixture to the temperature of 650-;
or directly heating the mixture of the potassium-containing compound, the molybdenum-containing compound and the phosphorus-containing compound or the mixture of the potassium-containing compound, the molybdenum-containing compound, the phosphorus-containing compound and the fluxing agent to the temperature of 650-1000 ℃ at the heating rate of 1-30 ℃/h, keeping the temperature for 5-80 hours to obtain a mixed melt, and then cooling to the temperature of 500-800 ℃, wherein the molar ratio of the potassium-containing compound, the molybdenum-containing compound and the phosphorus-containing compound to the fluxing agent is 1:1:2: 0-20;
the fluxing agent being essentially a self-fluxing agent, e.g. K2CO3、KF、KOH、K2O、KCl、MoF6、Mo(CO3)3、MoO3、MoCl6、P2O5Etc. and other composite fluxes, such as Mo (CO)3)3-P2O5、K2CO3-P2O5、MoO3-P2O5、K2O-P2O5、MoF6-P2O5、MoCl6-P2O5、KCl-P2O5、KF-P2O5、K2O-TeO2、K2CO3-TeO2、KF-TeO2、MoO3-TeO2、Mo(CO3)3-TeO2、MoF6-TeO2、P2O5-TeO2、MoF6-K2CO3、K2O-Mo(CO3)3、MoO3-K2CO3、KF-Mo(CO3)3、P2O5-MoO3-K2O、P2O5-MoF6-KF、P2O5-MoCl6-KCl、P2O5-TeO2-K2O or P2O5-TeO2-MoO3And the like.
The compound potassium molybdenum phosphate single-phase polycrystalline powder is prepared by a solid-phase synthesis method, and comprises the following steps: mixing a potassium-containing compound, a molybdenum-containing compound and a phosphorus-containing compound to obtain the compound molybdenum potassium phosphate by a solid-phase reaction method, wherein the molar ratio of potassium element in the potassium-containing compound, molybdenum element in the molybdenum-containing compound and phosphorus element in the phosphorus-containing compound is 4:5:2, uniformly mixing raw materials of the potassium-containing compound, the molybdenum-containing compound and the phosphorus-containing compound, grinding, putting the mixture into a muffle furnace, pre-burning to remove water and gas in the raw materials, cooling to room temperature, taking out the mixture after grinding, putting the mixture into the muffle furnace to calcine, heating to 900 ℃, keeping the temperature for 72 hours, cooling to room temperature, taking out and grinding to obtain the compound molybdenum potassium phosphate single-phase polycrystalline powder.
b. Preparing a potassium molybdenum phosphate seed crystal: slowly cooling the mixed melt obtained in the step a to room temperature at the speed of 0.5-10 ℃/h, and spontaneously crystallizing to obtain the potassium molybdenum phosphate seed crystal;
c. b, placing the crucible containing the mixed melt prepared in the step a into a crystal growth furnace, fixing the seed crystal obtained in the step b on a seed crystal rod, preheating the seed crystal from the top of the crystal growth furnace for 5-60 minutes, placing the seed crystal until the seed crystal is in contact with the liquid level of the mixed melt or the mixed melt for remelting, keeping the temperature for 5-60 minutes, and reducing the temperature to the saturation temperature at the rate of 1-60 ℃/h;
d. slowly cooling at the speed of 0.1-5 ℃/day, rotating the seed rod at the speed of 0-60rpm to grow crystals, lifting the crystals away from the surface of the mixed melt after the single crystals grow to the required size, cooling to room temperature at the speed of 1-80 ℃/h, and taking out the crystals from the hearth to obtain the molybdenum potassium phosphate nonlinear optical crystals.
The fluxing agent is Mo (CO)3)3-P2O5Mo (CO) in the system3)3And P2O5The molar ratio of (A) to (B) is 1-3: 2-5; k2CO3-P2O5In the system K2CO3And P2O5The molar ratio is 1-3: 3-6; MoO3-P2O5MoO in the system3And P2O5The molar ratio is 1-3: 2-5; k2O-P2O5In the system K2O and P2O5The molar ratio is 1-3: 3-6; MoF6-P2O5MoF in the system6And P2O5The molar ratio of (A) to (B) is 1-9: 2-5; MoCl6-P2O5MoCl in the system6And P2O5The molar ratio of (A) to (B) is 1-10: 2-5; KCl-P2O5KCl and P in the system2O5The molar ratio of (A) to (B) is 1-5: 2-5; KF-P2O5In the system KF and P2O5The molar ratio of (A) to (B) is 1-6: 2-5; k2O-TeO2In the system K2O and TeO2The molar ratio is 1-10: 3-6; k2CO3-TeO2In the system K2CO3And TeO2The molar ratio is 1-9: 3-6; KF-TeO2KF and TeO in the system2The molar ratio is 1-6: 3-6; MoO3-TeO2MoO in the system3And TeO2The molar ratio is 1-5: 3-6; mo (CO)3)3-TeO2Mo (CO) in the system3)3And TeO2The molar ratio is 2-5: 1-3; MoF6-TeO2MoF in the system6And K2CO3The molar ratio is 1-8: 3-6; MoO3-K2CO3MoO in the system3And K2CO3The molar ratio is 1-8: 3-6; KF-Mo (CO)3)3KF and Mo in the system2CO3The molar ratio is 1-10: 3-6; k2O-Mo(CO3)3In the system K2O and Mo (CO)3)3The molar ratio is 1-8: 3-6; p2O5-MoO3-K2P in O system2O5、MoO3And K2The molar ratio of O is 2-5:1-6: 3-8; p2O5-MoF6P in the-KF system2O5、MoF6The molar ratio of the KF to the KF is 2-5:1-6: 3-10; p2O5-MoCl6-KCl system P2O5、MoCl6The molar ratio of the KCl to the KCl is 2-5:1-6: 1-5; p2O5-TeO2-K2P in O system2O5、TeO2And K2The molar ratio of O is 2-5:1-6: 3-8; p2O5-TeO2-MoO3In the system P2O5、TeO2With MoO3The molar ratio is 2-5:1-9: 3-8.
The nonlinear optical crystal of potassium molybdenum phosphate prepared by the invention is characterized in that the chemical formula of the crystal is K4Mo5P2O22Molecular weight 262.51, not having a center of symmetry, belonging to orthorhombic system, space group C2221Cell parameter of
Molecular weight, its powder frequency doubling effect is about 1 times KDP (KH)2PO4)。
Because of using K in the process of growing the potassium molybdenum phosphate nonlinear optical crystal2CO3、KF、KOH、K2O、KCl、MoF6、Mo(CO3)3、MoO3、MoCl6、P2O5Isofluxing agents and also alloys such as Mo (CO)3)3-P2O5、K2CO3-P2O5、MoO3-P2O5、K2O-P2O5、MoF6-P2O5、MoCl6-P2O5、KCl-P2O5、KF-P2O5、K2O-TeO2、K2CO3-TeO2、KF-TeO2、MoO3-TeO2、Mo(CO3)3-TeO2、MoF6-TeO2、P2O5-TeO2、MoF6-K2CO3、K2O-Mo(CO3)3、MoO3-K2CO3、KF-Mo(CO3)3、P2O5-MoO3-K2O、P2O5-MoF6-KF、P2O5-MoCl6-KCl、P2O5-TeO2-K2O or P2O5-TeO2-MoO3Other composite cosolvents have high product purity, crystals are easy to grow and are transparent without wrapping, and the composite cosolvents have the advantages of higher growth speed, low cost, easy obtainment of crystals with larger size and the like; the obtained crystal has the advantages of wider light-transmitting wave band, higher hardness, good mechanical property, difficult cracking and deliquescence, easy processing and storage and the like. The nonlinear optical device prepared by the compound potassium molybdenum phosphate nonlinear optical crystal obtained by the method uses Nd-YAG Q-switched laser as a light source at room temperature, enters infrared light with the wavelength of 1064nm, outputs green laser with the wavelength of 532nm, and has the laser intensity equivalent to KDP (KH)2PO4) 1 times of the total weight of the composition.
Drawings
FIG. 1 shows the invention K4Mo5P2O22X-ray diffraction pattern of the powder.
FIG. 2 shows the invention K4Mo5P2O22Working principle diagram of nonlinear optical device made of crystal, wherein 1 is laser, 2 is emitted light beam, and 3 is K4Mo5P2O22Crystal, 4 is emergent light beam, and 5 is filter.
Detailed Description
The invention is described in detail below with reference to the following figures and examples:
example 1:
according to the reaction formula: 2K2CO3+5MoO3+P2O5→K4Mo5P2O22+2CO2↓ synthetic compound K4Mo5P2O22：
Will K2CO3、MoO3、P2O5In mole ratioWeighing the materials in a ratio of 2:5:1, putting the materials into a mortar, mixing and carefully grinding the materials, then putting the materials into an open corundum crucible with the diameter of 100mm multiplied by 100mm, putting the mixture into a muffle furnace, slowly heating the mixture to 300 ℃, keeping the temperature for 24 hours, cooling the mixture to room temperature, taking the mixture out, putting the mixture into the muffle furnace after the second grinding, heating the mixture to 750 ℃, keeping the temperature for 24 hours, cooling the mixture to room temperature, taking the mixture out, putting the mixture into the muffle furnace after the third grinding, keeping the temperature at 750 ℃ for 48 hours, taking the mixture out, grinding the mixture to obtain a compound molybdenum potassium phosphate single-phase polycrystalline powder, carrying out X-ray analysis on the product, and carrying out X-ray analysis on the obtained product to obtain an X-ray spectrogram and a molybdenum potassium phosphate K4Mo5P2O22The X-ray spectrograms obtained from the single crystal structures are consistent;
the obtained compound of potassium molybdenum phosphate K4Mo5P2O22Single-phase polycrystalline powder and fluxing agent MoF6-P2O5Molar ratio of massage K4Mo5P2O22:MoF6-P2O51:3, wherein MoF6And P2O5The molar ratio of the components is 3:5, the mixture is mixed and loaded into an opening platinum crucible with the diameter phi of 80mm multiplied by 80mm, the mixture is heated to 850 ℃ at the heating rate of 30 ℃/h and is kept at the constant temperature for 15 hours to obtain a mixed melt, and then the temperature is reduced to 650 ℃;
slowly cooling to room temperature at the speed of 0.5 ℃/h, and spontaneously crystallizing to obtain the potassium molybdenum phosphate seed crystal;
growing crystals in a compound melt: k to be obtained4Mo5P2O22Seed crystals are fixed on a seed crystal rod and are discharged from the top of a crystal growing furnace, the seed crystals are preheated on the surface of the mixed melt for 10 minutes and immersed in the liquid level, the seed crystals are melted back in the mixed melt, the temperature is kept for 30 minutes, and the temperature is quickly reduced to 650 ℃;
cooling at a rate of 2 ℃/day, rotating the seed rod at a speed of 10rpm, separating the crystal from the liquid surface after the crystal growth is finished, and cooling to room temperature at a rate of 10 ℃/hour to obtain the K with the size of 56mm multiplied by 40mm multiplied by 30mm4Mo5P2O22And (4) crystals.
In the reaction formula, the raw material potassium carbonate can be replaced by other potassium-containing salts such as potassium oxide, potassium chloride, potassium bromide, potassium nitrate, potassium oxalate, potassium hydroxide, potassium bicarbonate or potassium sulfate, the molybdenum carbonate can be replaced by other molybdenum-containing salts such as molybdenum oxide, molybdenum chloride, molybdenum bromide, molybdenum nitrate, molybdenum oxalate or molybdenum hydroxide, and the phosphorus pentoxide can be replaced by other phosphorus salts.
Example 2:
according to the reaction formula: 4KNO3+5MoO3+P2O5→K4Mo5P2O22+4NO2↑+2O2↓ synthetic compound K4Mo5P2O22：
Mixing KNO3、MoO3、P2O5Directly weighing raw materials according to a molar ratio of 4:5:1, and mixing the weighed raw materials with a fluxing agent MoO3-P2O5Mixing according to a molar ratio of 1:4, wherein MoO is3And P2O5The molar ratio of (1) is 3:5, the mixture is put into an open platinum crucible with the diameter of 80mm multiplied by 80mm, the temperature is raised to 800 ℃, the temperature is kept for 60 hours, mixed melt is obtained, and the temperature is cooled to 650 ℃;
slowly cooling to room temperature at the speed of 1.5 ℃/h, and spontaneously crystallizing to obtain the potassium molybdenum phosphate seed crystal;
k to be obtained4Mo5P2O22Seed crystals are fixed on a seed crystal rod and are discharged from the top of a crystal growing furnace, the seed crystals are preheated on the surface of the mixed melt for 10 minutes, and are immersed below the liquid level, so that the seed crystals are melted back in the mixed melt, the temperature is kept for 30 minutes, and the temperature is quickly reduced to 600 ℃ of saturation temperature;
slowly cooling at a speed of 1 ℃/day, not rotating a seed rod, lifting the crystal away from the surface of the melt after the crystal grows to a required size, cooling to room temperature at a speed of 20 ℃/h, and taking out the crystal from a hearth to obtain the K with the size of 36mm multiplied by 22mm multiplied by 15mm4Mo5P2O22And (4) crystals.
In the reaction formula, potassium nitrate can be replaced by potassium oxide or potassium chloride or potassium bromide or potassium carbonate or potassium oxalate or potassium hydroxide or potassium bicarbonate or potassium sulfate and other potassium-containing salts, molybdenum carbonate can be replaced by molybdenum oxide or molybdenum chloride or molybdenum bromide or molybdenum nitrate or molybdenum oxalate or molybdenum hydroxide and other molybdenum-containing salts, and phosphorus pentoxide can be replaced by other phosphorus salts.
Example 3:
according to the reaction formula: 4KOH +5MoO3+P2O5→2K4Mo5P2O22+2H2O ↓ [ O ] synthetic compound K4Mo5P2O22：
KOH and MoO3、P2O5Directly weighing raw materials according to a molar ratio of 4:5:2, and mixing the weighed raw materials with a fluxing agent KF-TeO2Mixing according to the molar ratio of 1:3, wherein KF and TeO are mixed2The molar ratio is 3:1, the mixture is put into an opening platinum crucible with the diameter of 80mm multiplied by 80mm, the temperature is raised to 780 ℃, the temperature is kept for 60 hours, mixed melt is obtained, and the temperature is lowered to 620 ℃;
slowly cooling to room temperature at the speed of 3.5 ℃/h, and spontaneously crystallizing to obtain the potassium molybdenum phosphate seed crystal;
k to be obtained4Mo5P2O22Seed crystals are fixed on a seed crystal rod and are discharged from the top of a crystal growing furnace, the seed crystals are preheated on the surface of the mixed melt for 15 minutes, and are immersed below the liquid level, so that the seed crystals are melted back in the mixed melt, the temperature is kept for 30 minutes, and the temperature is quickly reduced to saturation temperature 615 ℃;
slowly cooling at a speed of 3 ℃/day, rotating the seed crystal crucible at a rotating speed of 5rpm, lifting the crystal from the surface of the melt after the crystal grows to a required size, cooling to room temperature at a speed of 1 ℃/h, and taking out the crystal from a hearth to obtain the K with the size of 25mm multiplied by 24mm multiplied by 10mm4Mo5P2O22And (4) crystals.
In the reaction formula, potassium hydroxide can be replaced by potassium oxide or potassium chloride or potassium bromide or potassium nitrate or potassium oxalate or potassium carbonate or potassium bicarbonate or potassium sulfate and other potassium-containing salts, molybdenum carbonate can be replaced by molybdenum oxide or molybdenum chloride or molybdenum bromide or molybdenum nitrate or molybdenum oxalate or molybdenum hydroxide and other molybdenum-containing salts, and phosphorus pentoxide can be replaced by other phosphorus salts.
Example 4:
according to the reaction formula: 2K2SO4+5MoO3+P2O5→K4Mo5P2O22+2SO2↑+O2↓ synthetic compound K4Mo5P2O22：
Will K2SO4、MoO3、P2O5Directly weighing raw materials according to the mol ratio of 2:5:1, and mixing the weighed raw materials with a fluxing agent P2O5-TeO2Mixing according to a molar ratio of 1:3, wherein P is2O5And TeO2The molar ratio is 5:1, the mixture is put into an opening platinum crucible with the diameter of 80mm multiplied by 80mm, the temperature is raised to 750 ℃, the temperature is kept for 80 hours, mixed melt is obtained, and the temperature is lowered to 615 ℃;
slowly cooling to room temperature at the speed of 5 ℃/h, and spontaneously crystallizing to obtain the potassium molybdenum phosphate seed crystal;
k to be obtained4Mo5P2O22Seed crystals are fixed on a seed crystal rod and are discharged from the top of a crystal growing furnace, the seed crystals are preheated on the surface of the mixed melt for 20 minutes and immersed below the liquid level, so that the seed crystals are melted back in the mixed melt, the temperature is kept for 5 minutes, and the temperature is quickly reduced to 600 ℃ of saturation temperature;
then slowly cooling at the speed of 3 ℃/day, rotating the seed rod at the rotating speed of 15rpm, separating the crystal body from the surface of the melt after the crystal grows to the required size, cooling to room temperature at the speed of 15 ℃/h, and taking out the crystal from the hearth to obtain the K with the size of 35mm multiplied by 25mm multiplied by 20mm4Mo5P2O22And (4) crystals.
In the reaction formula, potassium sulfate as raw material can be replaced by potassium oxide or potassium chloride or potassium bromide or potassium carbonate or potassium oxalate or potassium hydroxide or potassium bicarbonate or potassium nitrate and other potassium-containing salts, molybdenum carbonate can be replaced by molybdenum oxide or molybdenum chloride or molybdenum bromide or molybdenum nitrate or molybdenum oxalate or molybdenum hydroxide and other molybdenum-containing salts, and phosphorus pentoxide can be replaced by other phosphorus salts.
Example 5
According to the reaction formula: 2K2CO3+5MoO3+2NH4H2PO4→K4Mo5P2O22+2NH3↑+2CO2↑+3H2O ↓ [ O ] synthetic compound K4Mo5P2O22：
Will K2CO3、MoO3、NH4H2PO4Directly weighing raw materials according to the mol ratio of 2:5:2, and mixing the weighed raw materials with a fluxing agent KF-TeO2Mixing according to the molar ratio of 1:2, wherein KF and TeO are2Loading into a platinum crucible with a phi of 80mm multiplied by 80mm at a molar ratio of 5:1, heating to 760 ℃, keeping the temperature for 80 hours to obtain a mixed melt, and cooling to 650 ℃;
slowly cooling to room temperature at the speed of 10 ℃/h, and spontaneously crystallizing to obtain the potassium molybdenum phosphate seed crystal;
fixing the obtained seed crystal on a seed crystal rod, preheating the seed crystal on the surface of the mixed melt for 25 minutes from the top of a crystal growth furnace, partially immersing the seed crystal below the liquid level, melting the seed crystal in the mixed melt back, keeping the temperature for 25 minutes, and rapidly cooling to 615 ℃ of saturation temperature;
cooling at a speed of 5 ℃/day, rotating the seed rod at a speed of 30rpm, lifting the crystal from the surface of the melt after the crystal grows to a required size, cooling to room temperature at a speed of 35 ℃/h, and taking out the crystal from the hearth to obtain the K with the size of 22mm multiplied by 32mm multiplied by 20mm4Mo5P2O22And (4) crystals.
The potassium chloride in the reaction formula can be replaced by potassium oxide or potassium sulfate or potassium bromide or potassium carbonate or potassium oxalate or potassium hydroxide or potassium bicarbonate or potassium nitrate and other potassium-containing salts, the molybdenum carbonate can be replaced by molybdenum oxide or molybdenum chloride or molybdenum bromide or molybdenum nitrate or molybdenum oxalate or molybdenum hydroxide and other molybdenum-containing salts, and the phosphorus pentoxide can be replaced by other phosphorus salts.
Example 6
According to the reaction formula: 4KNO3+5MoO3+2NH4H2PO4→K4Mo5P2O22+4NO2↑+2NH3↑3H2O↑+O2↓ synthetic compound K4Mo5P2O22：
Mixing KNO3、MoO3、NH4H2PO4Directly weighing raw materials according to a molar ratio of 4:5:2, and mixing the weighed raw materials with a fluxing agent KF-TeO2Mixing according to the molar ratio of 1:3, wherein KF and TeO are2The molar ratio is 5:1, the mixture is put into an opening platinum crucible with the diameter of 80mm multiplied by 80mm, the temperature is raised to 800 ℃, the temperature is kept for 5 hours to obtain mixed melt, and the temperature is lowered to 620 ℃;
slowly cooling to room temperature at the speed of 4.0 ℃/h, and spontaneously crystallizing to obtain the potassium molybdenum phosphate seed crystal;
k to be obtained4Mo5P2O22Seed crystals are fixed on a seed crystal rod and are discharged from the top of a crystal growing furnace, the seed crystals are preheated on the surface of the mixed melt for 20 minutes and immersed below the liquid level, the seed crystals are melted back in the mixed melt, the temperature is kept for 25 minutes, and the temperature is quickly reduced to the saturation temperature of 605 ℃;
then cooling at the speed of 3 ℃/day, rotating the seed rod at the rotating speed of 50rpm, separating the crystal body from the surface of the melt after the crystal grows to the required size, cooling to room temperature at the speed of 70 ℃/h, and taking out the crystal from the hearth to obtain the K with the size of 22mm multiplied by 21mm multiplied by 16mm4Mo5P2O22And (4) crystals.
The potassium bromide used as the raw material in the reaction formula can be replaced by other potassium-containing salts such as potassium oxide, potassium sulfate, potassium chloride, potassium carbonate, potassium oxalate, potassium hydroxide, potassium bicarbonate, potassium nitrate and the like, the molybdenum carbonate can be replaced by other molybdenum-containing salts such as molybdenum oxide, molybdenum chloride, molybdenum bromide, molybdenum nitrate, molybdenum oxalate, molybdenum hydroxide and the like, and the phosphorus pentoxide can be replaced by other phosphorus salts.
Example 7
According to the reaction formula: 2K2C2O4+5MoO3+P2O5→K4Mo5P2O22+2CO↑+2CO2↑
Synthesis of Compound K4Mo5P2O22：
Will K2C2O4、MoO3、P2O5Putting the mixture into a mortar according to the mol ratio of 2:5:1, mixing and carefully grinding the mixture, then putting the mixture into an open corundum crucible with the diameter of 100mm multiplied by 100mm, compacting the corundum crucible, putting the corundum crucible into a muffle furnace, slowly heating the mixture to the temperature of 500 ℃, keeping the temperature for 4 hours, taking out the crucible after cooling, taking out the sample, uniformly grinding the sample again, putting the sample into the crucible again, keeping the temperature for 48 hours again in the muffle furnace at the temperature of 750 ℃, taking out the sample, putting the sample into the mortar, smashing and grinding the sample to obtain the compound K4Mo5P2O22Carrying out X-ray analysis on the product to obtain an X-ray spectrogram and potassium molybdenum phosphate K4Mo5P2O22The X-ray spectrograms obtained from the single crystal structures are consistent; a
The synthesized compound K4Mo5P2O22With a fluxing agent K2O-TeO2Mixing according to a molar ratio of 1:3, wherein K2O and TeO2The molar ratio is 5:1, the mixture is put into an opening platinum crucible with the diameter of 80mm multiplied by 80mm, the temperature is raised to 900 ℃, the temperature is kept for 50 hours to obtain mixed melt, and the temperature is lowered to 750 ℃; slowly cooling to room temperature at the speed of 4.0 ℃/h, and spontaneously crystallizing to obtain the potassium molybdenum phosphate seed crystal;
k to be obtained4Mo5P2O22Seed crystals are fixed on a seed crystal rod and are discharged from the top of a crystal growing furnace, the seed crystals are preheated on the surface of the mixed melt for 20 minutes and immersed below the liquid level, the seed crystals are melted back in the mixed melt, the temperature is kept for 25 minutes, and the temperature is reduced to saturation temperature 715 ℃;
then cooling at the speed of 2 ℃/day, rotating the seed rod at the rotating speed of 28rpm, separating the crystal body from the surface of the melt after the crystal grows to the required size, cooling to room temperature at the speed of 25 ℃/h, and taking out the crystal from the hearth to obtain the K with the size of 30mm multiplied by 22mm multiplied by 15mm4Mo5P2O22And (4) crystals.
The potassium oxalate used as the raw material in the reaction formula can be replaced by potassium oxide or potassium sulfate or potassium bromide or potassium carbonate or potassium chloride or potassium hydroxide or potassium bicarbonate or potassium nitrate and other potassium-containing salts, the molybdenum carbonate can be replaced by molybdenum oxide or molybdenum chloride or molybdenum bromide or molybdenum nitrate or molybdenum oxalate or molybdenum hydroxide and other molybdenum-containing salts, and the phosphorus pentoxide can be replaced by other phosphorus salts.
Example 8
According to the reaction formula: 2K2O+5Mo(CO3)3+P2O5→K4Mo5P2O22+15CO2↓ synthetic compound K4Mo5P2O22：
Will K2O、Mo(CO3)3、P2O5Putting the raw materials and a fluxing agent K into a mortar according to the mol ratio of 2:5:12O-Mo(CO3)3-P2O5Mixing according to a molar ratio of 1:1, wherein P is2O5、MoO3And TeO2The mol ratio is 6:3:4, the mixture is put into an opening platinum crucible with the diameter of 80mm multiplied by 80mm, the temperature is raised to 760 ℃, the temperature is kept for 80 hours, mixed melt is obtained, and the temperature is reduced to 650 ℃;
slowly cooling to room temperature at the speed of 10 ℃/h, and spontaneously crystallizing to obtain the potassium molybdenum phosphate seed crystal;
fixing the obtained seed crystal on a seed crystal rod, preheating the seed crystal on the surface of the mixed melt for 25 minutes from the top of a crystal growth furnace, partially immersing the seed crystal below the liquid level, melting the seed crystal in the mixed melt back, keeping the temperature for 25 minutes, and rapidly cooling to 615 ℃ of saturation temperature;
cooling at a speed of 5 ℃/day, rotating the seed rod at a speed of 30rpm, lifting the crystal from the surface of the melt after the crystal grows to a required size, cooling to room temperature at a speed of 35 ℃/h, and taking out the crystal from the hearth to obtain the K with the size of 22mm multiplied by 32mm multiplied by 20mm4Mo5P2O22And (4) crystals.
In the reaction formula, potassium oxide can be replaced by potassium oxalate or potassium sulfate or potassium bromide or potassium carbonate or potassium chloride or potassium hydroxide or potassium bicarbonate or potassium nitrate and other potassium-containing salts, molybdenum carbonate can be replaced by molybdenum oxide or molybdenum chloride or molybdenum bromide or molybdenum nitrate or molybdenum oxalate or molybdenum hydroxide and other molybdenum-containing salts, and phosphorus pentoxide can be replaced by other phosphorus salts.
Example 9
Any of K obtained in examples 1 to 84Mo5P2O22Processing a frequency multiplier with 5mm × 5mm × 6mm size by crystal along matching direction, arranging at 3 position as shown in FIG. 2, using Q-switched Nd: YAG laser as light source at room temperature, emitting infrared beam 2 with 1064nm wavelength from Q-switched Nd: YAG laser 1, and emitting into K4Mo5P2O22The single crystal 3 generates green frequency doubling light with the wavelength of 532nm, the output intensity is 0.6 times of KDP under the same condition, the emergent light beam 4 contains infrared light with the wavelength of 1064nm and green light with the wavelength of 532nm, and green laser with the wavelength of 532nm is obtained after filtering by the filter 5.
Claims (9)
1. The compound of potassium molybdenum phosphate is characterized in that the chemical formula of the compound of potassium molybdenum phosphate is K4Mo5P2O22。
2. The method for preparing the compound of potassium molybdenum phosphate according to claim 1, comprising the steps of: and mixing a potassium-containing compound, a molybdenum-containing compound and a phosphorus-containing compound to prepare the compound potassium molybdenum phosphate by a solid-phase reaction method, wherein the molar ratio of potassium element in the potassium-containing compound, molybdenum element in the molybdenum-containing compound and phosphorus element in the phosphorus-containing compound is 4:5: 2.
3. The method for preparing the compound of potassium molybdenum phosphate according to claim 2, wherein the compound of potassium molybdenum phosphate is prepared by a solid-phase reaction method, comprising the steps of: uniformly mixing raw materials of a potassium-containing compound, a molybdenum-containing compound and a phosphorus-containing compound, grinding, putting into a muffle furnace, pre-burning to remove moisture and gas in the raw materials, cooling to room temperature, taking out, grinding, putting into the muffle furnace, and calcining to obtain the compound of the potassium molybdenum phosphate.
The potassium-containing compound comprises at least one of potassium hydroxide, potassium oxide and potassium salt; the potassium salt comprises at least one of potassium chloride, potassium bromide, potassium nitrate, potassium oxalate, potassium carbonate, potassium bicarbonate and potassium sulfate;
the molybdenum-containing compound comprises at least one of molybdenum oxide, molybdenum hydroxide and molybdenum salt; the molybdenum salt comprises at least one of molybdenum chloride, molybdenum bromide, molybdenum nitrate, molybdenum oxalate, molybdenum carbonate and molybdenum sulfate;
the phosphorus-containing compound is phosphorus pentoxide, phosphorus pentoxide and phosphorus salt; the phosphorus salt comprises at least one of phosphorus chloride, phosphorus bromide, phosphorus nitrate, phosphorus oxalate, phosphorus carbonate, ammonium dihydrogen phosphate and phosphorus sulfate.
4. The compound of potassium molybdenum phosphate and potassium molybdenum phosphate nonlinear optical crystal are characterized in that the chemical formula of the crystal is K4Mo5P2O22Molecular weight 262.51, no symmetry center, crystal belonging to orthorhombic system, space group C2221Cell parameter of
5. The method for preparing the molybdatopotassium phosphate nonlinear optical crystal as claimed in claim 4, wherein the molybdatopotassium phosphate nonlinear optical crystal is grown by a high temperature melt method or a czochralski method.
6. The method as claimed in claim 5, wherein the molybdenyl potassium phosphate nonlinear optical crystal is prepared by a high temperature melt method or a Czochralski method, and the process comprises:
a. heating the mixture of the compound of potassium molybdenum phosphate single-phase polycrystalline powder obtained in any one of claims 1 to 3 or the compound of potassium molybdenum phosphate single-phase polycrystalline powder obtained in any one of claims 1 to 3 and a fluxing agent to melt to obtain a mixed melt;
or directly heating a mixture of a potassium-containing compound, a molybdenum-containing compound and a phosphorus-containing compound or a mixture of the potassium-containing compound, the molybdenum-containing compound and the phosphorus-containing compound with a fluxing agent to melt to obtain a mixed melt;
b. b, placing the crucible containing the mixed melt prepared in the step a into a crystal growth furnace, fixing seed crystals on a seed crystal rod, putting the seed crystals down to be in contact with the liquid level of the mixed melt or in the mixed melt for remelting, and reducing the temperature to saturation temperature; cooling or growing at constant temperature to prepare the molybdenum potassium phosphate nonlinear optical crystal.
7. The method of claim 6, wherein the molar ratio of the compound of the single-phase polycrystalline powder of potassium molybdenum phosphate to the flux is 1: 0-20; or the molar ratio of the potassium-containing compound, the molybdenum-containing compound and the phosphorus-containing compound to the fluxing agent is 1:1:2: 0-20; the fluxing agent comprises at least one of potassium hydroxide, molybdenum hydroxide, phosphorus pentoxide, potassium oxide, molybdenum oxide, phosphorus pentoxide, potassium salt, molybdenum salt and phosphorus salt, lead oxide, and composite fluxing agent MoO3-P2O5、K2O-NH4H2PO4、MoF6-P2O5、KF-MoO3、P2O5-MoO3、P2O5-KF-MoO3One or more of them.
8. The method of claim 7, wherein the composite flux is MoO3-P2O5MoO in the system3And P2O5The molar ratio of (A) to (B) is 1-3: 2-5; k2O-NH4H2PO4In the system K2O and NH4H2PO4The molar ratio is 1-3: 3-6; MoF6-P2O5MoF in the system6And P2O5The molar ratio of (A) to (B) is 1-6: 2-5; KF-MoO3KF and MoO in the system3The molar ratio is 1-6: 3-6; p2O5-MoO3In the system P2O5With MoO3The molar ratio is 2-5: 1-3; p2O5-KF-MoO3In the system P2O5KF and MoO3The molar ratio is 2-5:1-6: 3-8.
9. Use of the molybdatopotassium phosphate nonlinear optical crystal according to claim 4, wherein the molybdatopotassium phosphate nonlinear optical crystal is used for preparing a frequency doubling generator, an upper frequency converter, a lower frequency converter or an optical parametric oscillator.
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