CN116254606A - Compound barium tin germanate and barium tin germanate nonlinear optical crystal, preparation method and application - Google Patents
Compound barium tin germanate and barium tin germanate nonlinear optical crystal, preparation method and application Download PDFInfo
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- CN116254606A CN116254606A CN202111519080.8A CN202111519080A CN116254606A CN 116254606 A CN116254606 A CN 116254606A CN 202111519080 A CN202111519080 A CN 202111519080A CN 116254606 A CN116254606 A CN 116254606A
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- 239000013078 crystal Substances 0.000 title claims abstract description 113
- 150000001875 compounds Chemical class 0.000 title claims abstract description 93
- 230000003287 optical effect Effects 0.000 title claims abstract description 38
- ITVXALCWBIYZPP-UHFFFAOYSA-N [Sn].[Ba] Chemical compound [Sn].[Ba] ITVXALCWBIYZPP-UHFFFAOYSA-N 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title abstract description 9
- -1 barium-tin-germanium Chemical compound 0.000 claims abstract description 79
- 239000002253 acid Substances 0.000 claims abstract description 61
- 239000000843 powder Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 11
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 55
- 229910008449 SnF 2 Inorganic materials 0.000 claims description 39
- 229910052593 corundum Inorganic materials 0.000 claims description 38
- 239000010431 corundum Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 33
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 32
- 229910052788 barium Inorganic materials 0.000 claims description 32
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 32
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 31
- 229910052732 germanium Inorganic materials 0.000 claims description 28
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 28
- 238000000227 grinding Methods 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 17
- 239000004570 mortar (masonry) Substances 0.000 claims description 15
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 12
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 10
- 150000002290 germanium Chemical class 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- 159000000009 barium salts Chemical class 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 5
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 claims description 3
- JHAFEVXNMDQGTR-UHFFFAOYSA-L C(C(=O)[O-])(=O)[O-].[Ge+2] Chemical compound C(C(=O)[O-])(=O)[O-].[Ge+2] JHAFEVXNMDQGTR-UHFFFAOYSA-L 0.000 claims description 3
- NZZJOHSPSIMUFV-UHFFFAOYSA-L C([O-])([O-])=O.[Ge+2] Chemical compound C([O-])([O-])=O.[Ge+2] NZZJOHSPSIMUFV-UHFFFAOYSA-L 0.000 claims description 3
- VXXCTRXMBKNRII-UHFFFAOYSA-L S(=O)(=O)([O-])[O-].[Ge+2] Chemical compound S(=O)(=O)([O-])[O-].[Ge+2] VXXCTRXMBKNRII-UHFFFAOYSA-L 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 238000002441 X-ray diffraction Methods 0.000 claims description 3
- GGBJMFNBQAJSMV-UHFFFAOYSA-L [Ge+2].C([O-])(O)=O.C([O-])(O)=O Chemical compound [Ge+2].C([O-])(O)=O.C([O-])(O)=O GGBJMFNBQAJSMV-UHFFFAOYSA-L 0.000 claims description 3
- WNPMJIKMURUYFG-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Ge+2].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[Ge+2].[N+](=O)([O-])[O-] WNPMJIKMURUYFG-UHFFFAOYSA-N 0.000 claims description 3
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 claims description 3
- 229910001620 barium bromide Inorganic materials 0.000 claims description 3
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 3
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 3
- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 claims description 3
- 229940094800 barium oxalate Drugs 0.000 claims description 3
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 claims description 3
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 3
- 238000005360 mashing Methods 0.000 claims description 3
- VJHDVMPJLLGYBL-UHFFFAOYSA-N tetrabromogermane Chemical compound Br[Ge](Br)(Br)Br VJHDVMPJLLGYBL-UHFFFAOYSA-N 0.000 claims description 3
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 3
- RYSQYJQRXZRRPH-UHFFFAOYSA-J tin(4+);dicarbonate Chemical compound [Sn+4].[O-]C([O-])=O.[O-]C([O-])=O RYSQYJQRXZRRPH-UHFFFAOYSA-J 0.000 claims description 3
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims description 3
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002083 X-ray spectrum Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 3
- 230000004907 flux Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 32
- 239000002994 raw material Substances 0.000 description 16
- 239000007858 starting material Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005303 weighing Methods 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
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/32—Titanates; Germanates; Molybdates; Tungstates
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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
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
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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
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/02—Production of homogeneous polycrystalline material with defined structure directly from the solid state
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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
- 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
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- 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
The invention relates to a barium-tin-germanium acid compound, a barium-tin-germanium acid nonlinear optical crystal, a preparation method and application thereof, wherein the chemical formulas of the compound and the crystal are BaSnOGEO 4 All belong to orthorhombic system, space group Pna2 1 The unit cell parameters are
α＝β＝γ＝90°，Z＝8 unit cell volume
Molecular weight 408.62, baSnOGEO 4 The powder has about 2-3 times KDP (KH) of frequency doubling effect under 1064nm laser irradiation 2 PO 4 ). The compound barium-tin-germanium acid is synthesized by adopting a high-temperature solid-phase reaction method, and the nonlinear optical crystal of the barium-tin-germanium acid grows by adopting a high-temperature solution method or a top seed crystal method, so that the nonlinear optical crystal is widely applied to optical devices in the fields of frequency doubling generators, upper or lower frequency converters, optical parametric oscillators, ferroelectrics, piezoelectrics, pyroelectric and the like.
Description
Technical Field
The invention relates to a novel nonlinear optical crystal material barium tin germanium acid, the chemical formula of which is BaSnOGEO 4 The preparation method of nonlinear optical crystal and powder belongs to the technical field of optical technology and crystal material technology.
Background
In recent years, the research of novel nonlinear optical crystal materials with large far infrared frequency doubling effect, wide transmission wave band, large optical damage threshold and stable physical and chemical properties gradually becomes a hot topic. The main nonlinear optical materials at present are: beta-BaB 2 O 4 (BBO) crystal, liB 3 O 5 (LBO) Crystal, csB 3 O 5 (CBO) crystals, csLiB 6 O 10 (CLBO) Crystal, KBe 2 BO 3 F 2 (KBBF) crystal, agGaS 2 (AGS) crystal, agGaSe 2 (AGSe) crystal and ZnGeP 2 (ZGP) crystals. Although the crystal growth techniques of these materials have grown to date, there are significant disadvantages: such as deliquescence of crystals, long growth period, serious lamellar growth habit, high price, small laser damage threshold, two-photon absorption and the like. Therefore, finding new nonlinear optical crystal materials remains a very important and arduous task.
The germanate crystal is an important semiconductor material and a middle infrared material, has wide attention on performance, and has wide application in the fields of illumination, display, military safety protection, laser medical treatment and the like. Because of the good comprehensive performance, the method is favorable for obtaining stronger nonlinear optical effect, and is an ideal choice of novel medium-far infrared nonlinear optical crystal.
Disclosure of Invention
It is an object of the present invention to provide a barium tin germanic acid compound.
The second purpose of the invention is to provide a preparation method of the barium tin germanium acid compound.
The invention further provides a barium tin germanic acid nonlinear optical crystal.
The invention aims at providing a preparation method of a barium-tin-germanium acid nonlinear optical crystal.
The invention aims to provide a fluxing agent system for growing a barium-tin-germanium acid nonlinear optical crystal.
The invention aims at providing an application of a barium tin germanic acid nonlinear optical crystal.
One of the objects of the present invention is achieved by:
the invention aims at providing a novel nonlinear optical material barium-tin-germanium acid compound, which is characterized in that the chemical formula of the crystal is BaSnOGEO 4 Molecular weight 408.62, which is an orthorhombic system, space group Pna2 1 The unit cell parameters are
α=β=γ=90°, z=8, unit cell volume
YAG Q-switched laser is used as light source at room temperature, and under 1064nm laser irradiation, the crystal has about powder frequency doubling capability of commercial crystal KDP (KH 2 PO 4 ) 2 to 3 times of the total weight of the steel sheet.
The second object of the invention is realized in that:
a preparation method of a barium tin germanic acid compound comprises the following steps:
a. under the condition of normal temperature and normal pressure, uniformly mixing element barium in a barium-containing compound, tin element in a tin-containing compound and germanium element in a germanium-containing compound in a ratio of 0.75-1.45:0.6-1.4:0.7-1.3, grinding for multiple times, putting the mixture into a clean corundum crucible, putting the corundum crucible carrying a sample into a muffle furnace, setting a furnace program, and preparing a sintered sample;
the barium-containing compound comprises at least one of a barium simple substance, barium oxide, barium peroxide and barium salt; the barium salt comprises at least one of barium fluoride, barium bromide, barium nitrate, barium oxalate, barium carbonate, barium sulfate and the like;
the tin-containing compound is at least one of tin oxide and tin salt; the germanium salt comprises at least one of tin chloride, tin bromide, tin nitrate, tin oxalate, tin carbonate and tin sulfate;
the germanium-containing compound is at least one of germanium oxide and germanium salt; the germanium salt comprises at least one of germanium chloride, germanium bromide, germanium nitrate, germanium oxalate, germanium carbonate, germanium bicarbonate and germanium sulfate;
the barium-tin-germanium acid compound can be prepared by adopting a vacuum high-temperature solid phase reaction method according to the following chemical reaction formula:
1)BaCO 3 +GeO 2 +SnO 2 →BaSnOGeO 4 +CO 2 ↑
2)2BaF 2 +2GeO 2 +2SnO 2 +O 2 →2BaSnOGeO 4 +2F 2 ↑
3)2BaCl 2 +2GeO 2 +2SnO 2 +O 2 →2BaSnOGeO 4 +2Cl 2 ↑
4)Ba(OH) 2 +GeO 2 +SnO 2 →BaSnOGeO 4 +H 2 O↑
5)BaSO 4 +GeO 2 +SnO 2 →BaSnOGeO 4 +SO 3 ↑
6)BaO+GeO 2 +SnO 2 →BaSnOGeO 4
7)2Ba(NO 3 ) 2 +2GeO 2 +2SnO 2 →2BaSnOGeO 4 +2NO 2 ↑+O 2 ↑
8)2BaCO 3 +2GeO 2 +2SnCO 3 +O 2 →2BaSnOGeO 4 +4CO 2 ↑
9)BaCO 3 +GeF 4 +SnO 2 +O 2 →BaSnOGeO 4 +CO 2 ↑+2F 2 ↑
10)BaCO 3 +SnF 2 +GeO 2 +O 2 →BaSnOGeO 4 +CO 2 ↑+F 2 ↑
11)BaO+GeO 2 +SnF 2 +O 2 →BaSnOGeO 4 +F 2 ↑
12)BaSO 4 +GeO 2 +SnF 2 +O 2 →BaSnOGeO 4 +SO 3 ↑+F 2 ↑
13)2BaSO 4 +2GeO 2 +2Sn(OH )2 +O 2 →2BaSnOGeO 4 +2SO 3 ↑+H 2 O↑
14)Ba(OH) 2 +GeO 2 +Sn(OH )2 →BaSnOGeO 4 +H 2 O↑
15)BaCO 3 +GeO 2 +Sn(CO 3 ) 2 →BaSnOGeO 4 +3CO 2 ↑
b. setting a muffle furnace procedure for sintering the sample in the step a, raising the temperature from room temperature to 400-700 ℃ at a speed of 5-10 ℃/min in a low-temperature stage, preserving the heat for 10 hours, raising the temperature to 1000-1400 ℃ at a speed of 1-5 ℃/min, and preserving the heat for 30-100 hours;
c. cooling at a rate of 1-10deg.C/h to room temperature, taking out the sample, mashing in a mortar, and grinding to obtain BaSnOGEO 4 Polycrystalline powder.
The third object of the present invention is achieved by:
the invention aims at providing a novel nonlinear optical material barium-tin-germanium acid crystal which is characterized in that the chemical formula of the crystal is BaSnOGEO 4 Molecular weight 408.62, having no symmetry center, belongs to orthorhombic system, and is space group Pna2 1 The unit cell parameters are
α=β=γ=90°, z=8, unit cell volume +.>
YAG Q-switched laser is used as light source at room temperature, and under 1064nm laser irradiation, the crystal has about powder frequency doubling capability of commercial crystal KDP (KH 2 PO 4 ) 2 to 3 times of the total weight of the steel sheet. Therefore, the compound barium tin germanic acid crystal has potential application value.
The fourth object of the present invention is achieved by:
a preparation method of barium tin germanic acid crystal comprises the following steps:
a. fully grinding the single-phase polycrystalline powder of the compound barium tin germanium acid obtained in any one of claims 1-3 or the mixture of the single-phase polycrystalline powder of the compound barium tin germanium acid obtained in any one of claims 1-3 and a fluxing agent in a normal temperature and normal pressure environment, putting the mixture into a clean corundum crucible, and transferring the corundum crucible with the sample into a muffle furnace;
or directly putting the mixture of barium element in the barium-containing compound, tin element in the tin-containing compound and germanium element in the germanium-containing compound in the ratio of 0.75-1.45:0.6-1.4:0.7-1.3 or the mixture of the barium-containing compound, the tin-containing compound, the germanium-containing compound and the fluxing agent into a clean corundum crucible, grinding for multiple times and then sintering for standby;
the barium-containing compound comprises at least one of a barium simple substance, barium oxide, barium peroxide and barium salt; the barium salt comprises at least one of barium fluoride, barium bromide, barium nitrate, barium oxalate, barium carbonate, barium sulfate and the like;
the tin-containing compound is at least one of tin oxide and tin salt; the germanium salt comprises at least one of tin chloride, tin bromide, tin nitrate, tin oxalate, tin carbonate and tin sulfate;
the germanium-containing compound is at least one of germanium oxide and germanium salt; the germanium salt comprises at least one of germanium chloride, germanium bromide, germanium nitrate, germanium oxalate, germanium carbonate, germanium bicarbonate and germanium sulfate;
the barium-tin-germanium acid crystal can be prepared by adopting a vacuum high-temperature solid-phase reaction method according to the following chemical reaction formula:
1)BaCO 3 +GeO 2 +SnO 2 →BaSnOGeO 4 +CO 2 ↑
2)2BaF 2 +2GeO 2 +2SnO 2 +O 2 →2BaSnOGeO 4 +2F 2 ↑
3)2BaCl 2 +2GeO 2 +2SnO 2 +O 2 →2BaSnOGeO 4 +2Cl 2 ↑
4)Ba(OH) 2 +GeO 2 +SnO 2 →BaSnOGeO 4 +H 2 O↑
5)BaSO 4 +GeO 2 +SnO 2 →BaSnOGeO 4 +SO 3 ↑
6)BaO+GeO 2 +SnO 2 →BaSnOGeO 4
7)2Ba(NO 3 ) 2 +2GeO 2 +2SnO 2 →2BaSnOGeO 4 +2NO 2 ↑+O 2 ↑
8)2BaCO 3 +2GeO 2 +2SnCO 3 +O 2 →2BaSnOGeO 4 +4CO 2 ↑
9)BaCO 3 +GeF 4 +SnO 2 +O 2 →BaSnOGeO 4 +CO 2 ↑+2F 2 ↑
10)BaCO 3 +SnF 2 +GeO 2 +O 2 →BaSnOGeO 4 +CO 2 ↑+F 2 ↑
11)BaO+GeO 2 +SnF 2 +O 2 →BaSnOGeO 4 +F 2 ↑
12)BaSO 4 +GeO 2 +SnF 2 +O 2 →BaSnOGeO 4 +SO 3 ↑+F 2 ↑
13)2BaSO 4 +2GeO 2 +2Sn(OH )2 +O 2 →2BaSnOGeO 4 +2SO 3 ↑+H 2 O↑
14)Ba(OH) 2 +GeO 2 +Sn(OH )2 →BaSnOGeO 4 +H 2 O↑
15)BaCO 3 +GeO 2 +Sn(CO 3 ) 2 →BaSnOGeO 4 +3CO 2 ↑
b. c, placing the sample ground and prepared in the step a into a muffle furnace, raising the temperature from room temperature to 400-700 ℃ at a speed of 5-10 ℃/min at a low temperature stage, preserving the temperature for 10 hours, raising the temperature to 1000-1700 ℃ at a speed of 1-5 ℃/min, and preserving the temperature for 30-100 hours;
c. cooling to room temperature at the speed of 0.5-10 ℃/h, taking out the sample, detecting and identifying the sample by an X-ray single crystal diffractometer, and confirming to prepare the barium-tin-germanic acid crystal.
The fifth object of the present invention is achieved by:
the chemical formula of the barium-tin-germanium acid crystal provided by the invention is BaSnOGEO 4 The method comprises the steps of carrying out a first treatment on the surface of the The preparation process comprises the following steps: uniformly mixing the barium-containing compound, stannizing and the compound germanium-containing compound raw materials, grinding, putting into a muffle furnace, heating in stages, preserving heat for a long time, and finally slowly cooling to obtain the barium-tin-germanium acid crystal.
The invention provides a method for preparing a fluxing agent of a barium-tin-germanium acid nonlinear optical crystal, which adopts a vacuum high-temperature solid-phase reaction method or a top seed crystal pulling method to grow the barium-tin-germanium acid nonlinear optical crystal, and comprises the following steps of:
a. the barium-tin-germanium acid nonlinear optical crystal is prepared by adopting a high-temperature solid-phase reaction method.
1) Grinding the single-phase polycrystalline powder of the compound barium tin germanium acid obtained in any one of claims 1-3 or the mixture of the single-phase polycrystalline powder of the compound barium tin germanium acid obtained in any one of claims 1-3 and a fluxing agent in an environment at normal temperature and normal pressure, putting the mixture into a clean corundum crucible, and transferring the corundum crucible with the sample into a muffle furnace;
or directly putting the mixture of barium element in the barium-containing compound, tin element in the tin-containing compound and germanium element in the germanium-containing compound in the ratio of 0.75-1.45:0.6-1.4:0.7-1.3 or the mixture of the barium-containing compound, the tin-containing compound, the germanium-containing compound and the fluxing agent into a clean corundum crucible, grinding for multiple times and then sintering for standby;
b. c, placing the sample ground and prepared in the step a into a muffle furnace, raising the temperature from room temperature to 400-700 ℃ at a speed of 5-10 ℃/min at a low temperature stage, preserving the temperature for 10 hours, raising the temperature to 1000-1700 ℃ at a speed of 1-5 ℃/min, and preserving the temperature for 30-100 hours;
c. cooling to room temperature at the speed of 0.5-10 ℃/h, taking out the sample, detecting and identifying the sample by an X-ray single crystal diffractometer, and confirming to prepare the barium-tin-germanic acid crystal.
The fluxing agent being predominantly a conventional fluxing agent, e.g. H 3 BO 3 、B 2 O 3 、Bi 2 O 3 、PbO、PbF 2 、MoO 3 、NaF、SnF 2 、BaF 2 、GeF 4 、KF、LiF、K 2 CO 3 、Na 2 CO 3 、Li 2 CO 3 、GeO 2 One or more of the following or a composite fluxing agent comprising H 3 BO 3 -NaF、H 3 BO 3 -PbO、H 3 BO 3 -PbF 2 、H 3 BO 3 -MoO 3 、H 3 BO 3 -SnF 2 、H 3 BO 3 -BaF 2 、H 3 BO 3 -GeF 4 、H 3 BO 3 -KF、H 3 BO 3 -LiF、H 3 BO 3 -K 2 CO 3 、H 3 BO 3 -Na 2 CO 3 、H 3 BO 3 -Li 2 CO 3 、PbO-PbF 2 、SnF 2 -GeO 2 、H 3 BO 3 -Bi 2 O 3 -NaF、H 3 BO 3 -PbO-PbF 2 、BaF 2 -SnF 2 -Bi 2 O 3 、BaF 2 -Bi 2 O 3 -MoO 3 、PbO-SnF 2 -MoO 3 、KF-H 3 BO 3 -PbF 2 One or more of the following.
The composite fluxing agent H 3 BO 3 H in the NaF System 3 BO 3 The molar ratio of the catalyst to NaF is 1-10:2-5; h 3 BO 3 H in PbO System 3 BO 3 The mol ratio of the catalyst to PbO is 1-10:1-4; h 3 BO 3 -PbF 2 H in the system 3 BO 3 With PbF 2 The molar ratio is 1-10:1-5; h 3 BO 3 -MoO 3 H in the system 3 BO 3 With MoO 3 The molar ratio is 1-10:2-8; h 3 BO 3 -SnF 2 H in the system 3 BO 3 With SnF 2 The molar ratio of (2) is 1-10:1-6; h 3 BO 3 -BaF 2 H in the system 3 BO 3 With BaF 2 The molar ratio of (2) is 1-10:1-3; h 3 BO 3 -GeF 4 H in the system 3 BO 3 With GeF 4 The molar ratio of (2) is 1-10:1-3.5; h 3 BO 3 H in-KF System 3 BO 3 The molar ratio of KF to KF is 1-10:1-5; h 3 BO 3 H in LiF System 3 BO 3 The molar ratio of LiF to LiF is 1-10:0.5-4; h 3 BO 3 -K 2 CO 3 H in the system 3 BO 3 And K is equal to 2 CO 3 The molar ratio is 1-10:1-4.5; h 3 BO 3 -Na 2 CO 3 H in the system 3 BO 3 With Na and Na 2 CO 3 The molar ratio is 1-10:0.5-2.5; h 3 BO 3 -Li 2 CO 3 H in the system 3 BO 3 With Li 2 CO 3 The molar ratio is 1-10:2-5; pbO-PbF 2 PbO and PbF in the system 2 The molar ratio is 1-4:1-5; snF (SnF) 2 -GeO 2 SnF in System 2 With GeO 2 The molar ratio is 1-6:0.5-3; h 3 BO 3 -Bi 2 O 3 H in the NaF System 3 BO 3 、Bi 2 O 3 The molar ratio of the catalyst to NaF is 1-10:1-4:2-5; h 3 BO 3 -PbO-PbF 2 H in the system 3 BO 3 PbO and PbF 2 The molar ratio is 1-10:1-4:1-5; baF (Baf) 2 -SnF 2 -Bi 2 O 3 BaF in System 2 、SnF 2 With Bi 2 O 3 The molar ratio is 1-3:1-6:1-4; baF (Baf) 2 -Bi 2 O 3 -MoO 3 BaF in System 2 、Bi 2 O 3 With MoO 3 The molar ratio is 1-3:1-4:2-8; pbO-SnF 2 -MoO 3 PbO and SnF in the system 2 With MoO 3 The molar ratio is 1-4:1-6:2-8; KF-H 3 BO 3 -PbF 2 KF, H in the system 3 BO 3 With PbF 2 The molar ratio is 1-5:1-10:1-5.
b. And preparing the barium-tin-germanium acid nonlinear optical crystal by adopting a top seed crystal pulling method.
1) Heating the single-phase polycrystalline powder of the compound barium tin germanium acid obtained in any one of claims 1-3 or the mixture of the single-phase polycrystalline powder of the compound barium tin germanium acid obtained in any one of claims 1-3 and a fluxing agent to melt to obtain mixed melt, and cooling or growing at constant temperature to prepare a compound barium tin germanium acid crystal;
or directly heating the mixture of barium in the barium-containing compound, tin in the tin-containing compound and germanium in the germanium-containing compound in the ratio of 0.75-1.45:0.6-1.4:0.7-1.3 or the mixture of the barium-containing compound, the tin-containing compound, the germanium-containing compound and the fluxing agent to melt to obtain a mixed solution, and cooling or growing at constant temperature to prepare the barium-tin-germanium acid crystal.
2) Preparing barium tin germanic acid seed crystal: slowly cooling the mixed solution obtained in the step a to room temperature at a speed of 0.5-10 ℃/h, and spontaneously crystallizing to obtain barium-tin-germanium acid seed crystal;
3) C, placing the crucible containing the mixed solution prepared in the step a into a crystal growth furnace, fixing the seed crystal obtained in the step b on a seed rod, preheating the seed crystal for 5-100 minutes, lowering the seed crystal to be in contact with the liquid surface of the mixed solution or the mixed solution for remelting, keeping the temperature for 5-60 minutes, and lowering the temperature to the saturation temperature at a speed of 0.1-10 ℃/h.
4) Then slowly cooling at the speed of 0.1-5 ℃/day, and rotating a seed rod or a rotating crucible at the rotating speed of 0-60 rpm to perform crystal growth; after the monocrystal grows to the required size, the crystal is lifted off the surface of the mixed molten liquid, cooled to room temperature at the speed of 1-80 ℃/h, and then taken out of a hearth, thus obtaining the barium-tin-germanium acid nonlinear optical crystal.
The fluxing agent being predominantly a conventional fluxing agent, e.g. H 3 BO 3 、B 2 O 3 、Bi 2 O 3 、PbO、PbF 2 、MoO 3 、NaF、SnF 2 、BaF 2 、GeF 4 、KF、LiF、K 2 CO 3 、Na 2 CO 3 、Li 2 CO 3 、GeO 2 One or more of the following or a composite fluxing agent comprising H 3 BO 3 -NaF、H 3 BO 3 -PbO、H 3 BO 3 -PbF 2 、H 3 BO 3 -MoO 3 、H 3 BO 3 -SnF 2 、H 3 BO 3 -BaF 2 、H 3 BO 3 -GeF 4 、H 3 BO 3 -KF、H 3 BO 3 -LiF、H 3 BO 3 -K 2 CO 3 、H 3 BO 3 -Na 2 CO 3 、H 3 BO 3 -Li 2 CO 3 、PbO-PbF 2 、SnF 2 -GeO 2 、H 3 BO 3 -Bi 2 O 3 -NaF、H 3 BO 3 -PbO-PbF 2 、BaF 2 -SnF 2 -Bi 2 O 3 、BaF 2 -Bi 2 O 3 -MoO 3 、PbO-SnF 2 -MoO 3 、KF-H 3 BO 3 -PbF 2 One or more of the following.
The composite fluxing agent H 3 BO 3 H in the NaF System 3 BO 3 The molar ratio of the catalyst to NaF is 1-10:2-5; h 3 BO 3 H in PbO System 3 BO 3 The mol ratio of the catalyst to PbO is 1-10:1-4; h 3 BO 3 -PbF 2 H in the system 3 BO 3 With PbF 2 The molar ratio is 1-10:1-5; h 3 BO 3 -MoO 3 H in the system 3 BO 3 With MoO 3 The molar ratio is 1-10:2-8; h 3 BO 3 -SnF 2 H in the system 3 BO 3 With SnF 2 The molar ratio of (2) is 1-10:1-6; h 3 BO 3 -BaF 2 H in the system 3 BO 3 With BaF 2 The molar ratio of (2) is 1-10:1-3; h 3 BO 3 -GeF 4 H in the system 3 BO 3 With GeF 4 The molar ratio of (2) is 1-10:1-3.5; h 3 BO 3 H in-KF System 3 BO 3 The molar ratio of KF to KF is 1-10:1-5; h 3 BO 3 H in LiF System 3 BO 3 The molar ratio of LiF to LiF is 1-10:0.5-4; h 3 BO 3 -K 2 CO 3 H in the system 3 BO 3 And K is equal to 2 CO 3 The molar ratio is 1-10:1-4.5; h 3 BO 3 -Na 2 CO 3 H in the system 3 BO 3 With Na and Na 2 CO 3 The molar ratio is 1-10:0.5-2.5; h 3 BO 3 -Li 2 CO 3 H in the system 3 BO 3 With Li 2 CO 3 The molar ratio is 1-10:2-5; pbO-PbF 2 PbO and PbF in the system 2 The molar ratio is 1-4:1-5; snF (SnF) 2 -GeO 2 SnF in System 2 With GeO 2 The molar ratio is 1-6:0.5-3; h 3 BO 3 -Bi 2 O 3 H in the NaF System 3 BO 3 、Bi 2 O 3 The molar ratio of the catalyst to NaF is 1-10:1-4:2-5; h 3 BO 3 -PbO-PbF 2 H in the system 3 BO 3 PbO and PbF 2 The molar ratio is 1-10:1-4:1-5; baF (Baf) 2 -SnF 2 -Bi 2 O 3 BaF in System 2 、SnF 2 With Bi 2 O 3 The molar ratio is 1-3:1-6:1-4; baF (Baf) 2 -Bi 2 O 3 -MoO 3 BaF in System 2 、Bi 2 O 3 With MoO 3 The molar ratio is 1-3:1-4:2-8; pbO-SnF 2 -MoO 3 PbO and SnF in the system 2 With MoO 3 The molar ratio is 1-4:1-6:2-8; KF-H 3 BO 3 -PbF 2 KF, H in the system 3 BO 3 With PbF 2 The molar ratio is 1-5:1-10:1-5.
The sixth object of the present invention is achieved by:
the barium-tin-germanic acid crystal is suitable for middle-infrared band laser frequency doubling crystals, electro-optic crystals, infrared communication devices and infrared laser guidance devices, and can be widely applied to optical devices and the like in the fields of frequency doubling generators, upper or lower frequency converters, optical parametric oscillators, ferroelectrics, piezoelectrics, pyroelectric and the like.
Drawings
FIG. 1 shows a compound BaSnOGEO prepared according to the invention 4 Theoretical X-ray spectrogram of the crystal.
FIG. 2 shows BaSnOGEO of the invention 4 A crystal structure diagram;
FIG. 3 shows BaSnOGEO of the invention 4 Working principle diagram of crystal-made nonlinear optical device, in which 1 is laser, 2 is emitted light beam, 3 is BaSnOGEO 4 The crystal, 4 is the outgoing light beam, 5 is the filter.
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.
Example 1
Preparing barium-tin-germanic acid polycrystalline powder by adopting a high-temperature solid phase reaction:
0.218g of BaCO as starting material was weighed under normal temperature and pressure conditions 3 ,0.116g GeO 2 And 0.166g SnO 2 (i.e. BaCO 3 ：GeO 2 ：SnO 2 The molar ratio of (1:1:1), mixing the raw materials uniformly, placing the raw materials in a mortar for careful grinding, placing the mixture in a clean corundum crucible, placing the corundum crucible in a muffle furnace, heating to 400 ℃ at the speed of 8 ℃/min, preserving heat for 10 hours, heating to 900 ℃ at the speed of 5 ℃/min, preserving heat for 50 hours, heating to 1200 ℃ at the speed of 3 ℃/min, preserving heat for 72 hours, and cooling to room temperature at the speed of 10 ℃/min to obtain the barium-tin-germanic acid polycrystalline powder.
Preparing barium-tin-germanic acid crystals by adopting a high-temperature solid phase reaction:
0.1413g of BaCO as starting material was weighed under normal temperature and pressure 3 ,0.07497g GeO 2 、0.1080g SnO 2 And 0.1757g PbF 2 (i.e. BaCO 3 ：GeO 2 ：SnO 2 ：PbF 2 The molar ratio of (1:1:1:1), mixing the raw materials uniformly, placing in a mortar for careful grinding, placing in a clean corundum crucible, placing the corundum crucible in a muffle furnace, heating to 400 ℃ at a speed of 8 ℃/min, preserving heat for 10 hours, heating to 900 ℃ at a speed of 5 ℃/min, preserving heat for 50 hours, and finally heating to 3 ℃ againAnd (3) raising the temperature to 1300 ℃ at the speed of C/min, preserving heat for 72h, and then cooling to room temperature at the speed of 5 ℃ per h to obtain the barium-tin-germanium acid crystal.
Example 2
Preparing barium-tin-germanic acid polycrystalline powder by adopting a high-temperature solid-phase reaction;
0.2506g of BaCO as starting material was weighed under normal temperature and pressure 3 ,0.1021g GeO 2 And 0.1421g SnO 2 (i.e. BaCO 3 ：GeO 2 ：SnO 2 The molar ratio of (2) is 1.3:1:1), the raw materials are mixed uniformly and placed in a mortar for careful grinding, then the mixture is placed in a clean corundum crucible, the corundum crucible is placed in a muffle furnace, the temperature is increased to 400 ℃ at the speed of 8 ℃/min, the heat is preserved for 10 hours, the temperature is increased to 900 ℃ at the speed of 5 ℃/min, the heat is preserved for 50 hours, the temperature is increased to 1200 ℃ at the speed of 3 ℃/min, the heat is preserved for 72 hours, and the temperature is reduced to room temperature at the speed of 10 ℃/min, so that the polycrystalline powder with the main phase of barium-tin-germanium acid is obtained.
Preparing barium-tin-germanic acid crystals by adopting a high-temperature solid phase reaction:
0.2022g of BaCO as starting material was weighed under normal temperature and pressure 3 ,0.08246g GeO 2 、0.1188g SnO 2 And 0.2091g PbF 2 (i.e. BaCO 3 ：GeO 2 ：SnO 2 ：PbF 2 The molar ratio of (2) is 1.3:1:1:0.5), the raw materials are mixed uniformly and placed in a mortar for careful grinding, then the mixture is placed in a clean corundum crucible, the corundum crucible is placed in a muffle furnace, the temperature is increased to 400 ℃ at the speed of 8 ℃/min, the temperature is kept for 10 hours, the temperature is increased to 900 ℃ at the speed of 5 ℃/min, the temperature is kept for 50 hours, the temperature is increased to 1350 ℃ at the speed of 3 ℃/min, the temperature is kept for 72 hours, and the temperature is reduced to the room temperature at the speed of 5 ℃/h, so that part of barium-tin-germanium acid crystals are obtained.
Example 3
Preparing barium-tin-germanic acid polycrystalline powder by adopting a high-temperature solid-phase reaction;
0.2477g of BaCO as starting material was weighed under normal temperature and pressure conditions 3 ,0.1010g GeO 2 And 0.1513g SnF 2 (i.e. BaCO 3 ：GeO 2 ：SnO 2 The molar ratio of (1:1:1), the raw materials are uniformly mixed and placed in a mortar for youngFine grinding, placing into a clean corundum crucible, placing the corundum crucible into a muffle furnace, heating to 400 ℃ at a speed of 8 ℃/min, preserving heat for 10 hours, heating to 900 ℃ at a speed of 5 ℃/min, preserving heat for 50 hours, heating to 1000 ℃ at a speed of 3 ℃/min, preserving heat for 72 hours, and cooling to room temperature at a speed of 10 ℃/min to obtain the polycrystalline powder with barium-tin-germanium acid as a main phase.
Preparing barium-tin-germanic acid crystals by adopting a high-temperature solid phase reaction:
0.2003g of BaCO as starting material was weighed under normal temperature and pressure 3 ,0.08169g GeO 2 、0.1223g SnF 2 And 0.09571g PbF 2 (i.e. BaCO 3 ：GeO 2 ：SnF 2 ：PbF 2 The molar ratio of (2) is 1.5:1:1:0.5), the raw materials are mixed uniformly and placed in a mortar for careful grinding, then the mixture is placed in a clean corundum crucible, the corundum crucible is placed in a muffle furnace, the temperature is increased to 400 ℃ at the speed of 8 ℃/min, the temperature is kept for 10 hours, the temperature is increased to 900 ℃ at the speed of 5 ℃/min, the temperature is kept for 50 hours, the temperature is increased to 1100 ℃ at the speed of 3 ℃/min, the temperature is kept for 72 hours, and the temperature is reduced to the room temperature at the speed of 5 ℃/h, so that part of barium-tin-germanium acid crystals are obtained.
Example 4
Preparing barium-tin-germanic acid polycrystalline powder by adopting a high-temperature solid-phase reaction;
weighing 0.2273g BaCO as the starting material at normal temperature and pressure 3 ,0.1391g GeO 2 And 0.1336g SnO 2 (i.e. BaCO 3 ：GeO 2 ：SnO 2 The molar ratio of (2) is 1:1.5:1), the raw materials are mixed uniformly and placed in a mortar for careful grinding, then the mixture is placed in a clean corundum crucible, the corundum crucible is placed in a muffle furnace, the temperature is raised to 600 ℃ at the speed of 5 ℃/min, the heat is preserved for 10 hours, the temperature is raised to 900 ℃ at the speed of 4 ℃/min, the heat is preserved for 50 hours, the temperature is raised to 1250 ℃ at the speed of 3 ℃/min, the heat is preserved for 72 hours, and the temperature is lowered to room temperature at the speed of 10 ℃/min, so that the polycrystalline powder with the main phase of barium-tin-germanium acid is obtained.
Preparing barium-tin-germanic acid crystals by adopting a high-temperature solid phase reaction:
0.1868g BaCO was weighed out as a starting material under normal temperature and pressure conditions 3 ,0.1143g GeO 2 、0.1097g SnO 2 And 0.0893g PbF 2 (i.e. BaCO 3 ：GeO 2 ：SnO 2 ：PbF 2 The molar ratio of (2) is 1:1.5:1:0.5), the raw materials are mixed uniformly and placed in a mortar for careful grinding, then the mixture is placed in a clean corundum crucible, the corundum crucible is placed in a muffle furnace, the temperature is raised to 600 ℃ at the speed of 5 ℃/min, the temperature is kept for 10 hours, the temperature is raised to 900 ℃ at the speed of 4 ℃/min, the temperature is kept for 50 hours, the temperature is raised to 1250 ℃ at the speed of 3 ℃/min, the temperature is kept for 72 hours, and the temperature is lowered to the room temperature at the speed of 5 ℃/h, so that the polycrystalline powder with the main phase of barium-tin-germanium acid is obtained.
Example 5
Preparing barium-tin-germanic acid polycrystalline powder by adopting a high-temperature solid-phase reaction;
0.2006g of BaCO as starting material was weighed under normal temperature and pressure 3 ,0.1227g GeO 2 And 0.1767g SnO 2 (i.e. BaCO 3 ：GeO 2 ：SnO 2 The molar ratio of (2) is 1:1.5:1.5), the raw materials are mixed uniformly and placed in a mortar for careful grinding, then the mixture is placed in a clean corundum crucible, the corundum crucible is placed in a muffle furnace, the temperature is raised to 800 ℃ at the speed of 5 ℃/min, the temperature is kept for 10 hours, the temperature is raised to 1050 ℃ at the speed of 4 ℃/min, the temperature is kept for 50 hours, the temperature is raised to 1350 ℃ at the speed of 3 ℃/min, the temperature is kept for 72 hours, and the temperature is lowered to room temperature at the speed of 10 ℃/min, so that the polycrystalline powder with partial peak of barium-tin-germanium acid is obtained.
Preparing barium-tin-germanic acid crystals by adopting a high-temperature solid phase reaction:
0.1273g of BaCO as starting material was weighed under normal temperature and pressure 3 ,0.0779g GeO 2 、0.1122g SnO 2 And 0.1826g PbF 2 (i.e. BaCO 3 ：GeO 2 ：SnO 2 ：PbF 2 The molar ratio of (2) is 1:1.5:1.5:1.5), the raw materials are mixed uniformly and placed in a mortar for careful grinding, then placed in a clean corundum crucible, then placed in a muffle furnace, heated to 600 ℃ at a speed of 5 ℃/min, kept at the temperature for 10 hours, heated to 900 ℃ at a speed of 4 ℃/min, kept at the temperature for 50 hours, finally heated to 1250 ℃ at a speed of 3 ℃/min, kept at the temperature for 72 hours, then cooled to room temperature at a speed of 5 ℃/h, and not completely heatedMelting to obtain a small amount of barium-tin-germanium acid crystals.
Example 6
Preparing barium-tin-germanic acid polycrystalline powder by adopting a high-temperature solid-phase reaction;
0.2008g of Ba (OH) as a starting material was weighed under normal temperature and pressure conditions 2 ,0.1226g GeO 2 And 0.1766g SnO 2 (i.e. BaCO 3 ：GeO 2 ：SnO 2 The molar ratio of (1:1:1), mixing the raw materials uniformly, placing the raw materials in a mortar for careful grinding, placing the mixture into a clean corundum crucible, placing the corundum crucible into a muffle furnace, heating to 300 ℃ at a speed of 5 ℃/min, preserving heat for 10 hours, heating to 7 ℃ at a speed of 4 ℃/min, preserving heat for 50 hours, heating to 950 ℃ at a speed of 3 ℃/min, preserving heat for 72 hours, and cooling to room temperature at a speed of 10 ℃/min to obtain the polycrystalline powder with partial peak of barium tin germanium acid.
Preparing barium-tin-germanic acid crystals by adopting a high-temperature solid phase reaction:
0.1088g of Ba (OH) as a starting material was weighed under normal temperature and pressure conditions 2 ,0.0997g GeO 2 、0.1436g SnO 2 And 0.1480g Bi 2 O 3 (i.e. BaCO 3 ：GeO 2 ：SnO 2 ：Bi 2 O 3 The molar ratio of (2) is 1:1.5:1.5:0.5), the raw materials are mixed uniformly and placed in a mortar for careful grinding, then the mixture is placed in a clean corundum crucible, the corundum crucible is placed in a muffle furnace, the temperature is raised to 600 ℃ at the speed of 5 ℃/min, the temperature is kept for 10 hours, the temperature is raised to 900 ℃ at the speed of 4 ℃/min, the temperature is kept for 50 hours, the temperature is raised to 950 ℃ at the speed of 3 ℃/min, the temperature is kept for 72 hours, the temperature is lowered to the room temperature at the speed of 5 ℃/h, and the mixture is not completely melted, so that a small amount of barium-tin-germanium acid crystals are obtained.
Example 7:
BaCO is carried out 3 、GeO 2 、SnO 2 According to 1:1:1, mixing and grinding, then placing into an open corundum crucible with phi of 100mm multiplied by 100mm, placing into a muffle furnace, slowly heating to 900 ℃, keeping the temperature for 24 hours, taking out the crucible after cooling, taking out the sample, grinding again uniformly, and placing into the crucible, and finally placing into the muffle furnaceKeeping the temperature at 1200 ℃ for 48 hours, taking out the mixture, putting the mixture into a mortar, and mashing and grinding the mixture to obtain BaSnOGEO 4 Compound, X-ray analysis of the product to obtain X-ray spectrum and barium stannic germanium acid BaSnOGEO 4 The X-ray spectrogram obtained by the single crystal structure is consistent;
the obtained compound of barium tin germanate BaSnOGEO 4 Single phase polycrystalline powder and fluxing agent HBO 3 Mixing KF according to a molar ratio of 1:5:3, loading into an open corundum crucible with phi of 80mm multiplied by 80mm, heating to 900 ℃ at a heating rate of 5 ℃/h, keeping the temperature for 15 hours to obtain a mixed melt, and cooling to 850 ℃;
slowly cooling to room temperature at a speed of 0.5 ℃/h, and obtaining barium-tin-germanium acid seed crystal through spontaneous crystallization; growing crystals in a compound melt: the obtained BaSnOGEO 4 The seed crystal is fixed on a seed rod from the top of a crystal growth furnace, the seed crystal is preheated on the surface of the mixed molten liquid for 10 minutes and immersed into the liquid surface, the seed crystal is remelted in the mixed molten liquid, the temperature is kept for 30 minutes, and the temperature is reduced to the saturation temperature of 862 ℃ at the speed of 10 ℃/h;
then cooling at a rate of 1 ℃/day, rotating the seed rod at a rotating 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 BaSnOGEO with a certain size 4 And (5) a crystal.
In the reaction formula, the carbonate of the raw materials can be replaced by oxide, nitrate, oxalate or hydroxide, tin oxide can be replaced by other tin salts, and germanium oxide can be replaced by other germanium salts.
Example 8:
any of the BaSnOGEO obtained in examples 1-7 4 After the crystal is further grown to a larger crystal, a frequency doubling device with the size of 5mm multiplied by 6mm is processed according to the matching direction, and is arranged at a position of 3 as shown in figure 3, at room temperature, a Q-switched Nd-YAG laser is used as a light source, the incident wavelength is 1064nm, and an infrared beam 2 with the wavelength of 1064nm is emitted by the Q-switched Nd-YAG laser 1 to be injected into BaSnOGEO 4 Single crystal 3 for generating green frequency doubling light with 532nm wavelength, the output intensity is 2-3 times of that of KDP with the same condition, and the outgoing light beam 4 contains light with 1064nm wavelengthAnd 532nm green light, and filtering by a filter 5 to obtain a green laser with 532nm wavelength.
Claims (10)
1. A barium-tin-germanium acid compound is characterized in that the chemical formula of the barium-tin-germanium acid compound is BaSnOGEO 4 Molecular weight 408.62, having no symmetry center, belongs to orthorhombic system, and is space group Pna2 1 The unit cell parameters are
α=β=γ=90°, z=8, unit cell volume
2. The method for preparing the compound barium tin germanium acid according to claim 1, which is characterized by comprising the following steps: mixing a barium-containing compound, a tin-containing compound and a germanium-containing compound, and preparing the compound barium-tin-germanium acid by adopting a high-temperature solid-phase reaction method, wherein the molar ratio of the element barium in the barium-containing compound to the element tin in the tin-containing compound to the element germanium in the germanium-containing compound is 0.75-1.45:0.6-1.4:0.7-1.3.
The barium-containing compound comprises at least one of a barium simple substance, barium oxide, barium peroxide and barium salt; the barium salt comprises at least one of barium fluoride, barium bromide, barium nitrate, barium oxalate, barium carbonate, barium sulfate and the like;
the tin-containing compound is at least one of tin oxide and tin salt; the germanium salt comprises at least one of tin chloride, tin bromide, tin nitrate, tin oxalate, tin carbonate and tin sulfate;
the germanium-containing compound is at least one of germanium oxide and germanium salt; the germanium salt comprises at least one of germanium chloride, germanium bromide, germanium nitrate, germanium oxalate, germanium carbonate, germanium bicarbonate and germanium sulfate.
3. The method for preparing the compound barium tin germanium acid according to claim 2, wherein the compound barium tin germanium acid is prepared by adopting a high-temperature solution reaction method or a pulling method, and the specific operation steps are as follows:
a. under the condition of normal temperature and normal pressure, uniformly mixing element barium in a barium-containing compound, tin element in a tin-containing compound and germanium element in a germanium-containing compound in a ratio of 0.75-1.45:0.6-1.4:0.7-1.3, grinding for multiple times, putting the mixture into a clean corundum crucible, putting the corundum crucible carrying a sample into a muffle furnace, setting a furnace program, and preparing a sintered sample;
b. setting a muffle furnace procedure for sintering the sample in the step a, raising the temperature from room temperature to 400-700 ℃ at a speed of 5-10 ℃/min in a low-temperature stage, preserving the heat for 10-20 hours, raising the temperature to 1000-1400 ℃ at a speed of 1-5 ℃/min, and preserving the heat for 30-100 hours;
c. cooling at a rate of 1-10deg.C/h to room temperature, taking out the sample, mashing in a mortar, and grinding to obtain BaSnOGEO 4 Polycrystalline powder, performing X-ray analysis on the obtained compound barium stannum germanic acid polycrystalline powder to obtain an X-ray diffraction pattern and BaSnOGEO analyzed by single crystal structure 4 The theoretical X-ray spectra are substantially identical.
4. A compound barium-tin-germanium acid nonlinear optical crystal is characterized in that the chemical formula of the crystal is BaSnOGEO 4 Molecular weight 408.62, having no symmetry center, belongs to orthorhombic system, and is space group Pna2 1 The unit cell parameters are
α=β=γ=90°, z=8, unit cell volume
5. The method for preparing a compound barium-tin-germanium acid nonlinear optical crystal according to claim 4, wherein the crystal is grown by a high-temperature solution reaction method or a top seed crystal pulling method.
6. The method according to claim 5, wherein the specific operation of preparing the barium tin germanic acid nonlinear optical crystal by the high-temperature solution reaction method is carried out by the following steps:
a. fully grinding the single-phase polycrystalline powder of the compound barium tin germanium acid obtained in any one of claims 1-3 or the mixture of the single-phase polycrystalline powder of the compound barium tin germanium acid obtained in any one of claims 1-3 and a fluxing agent in a normal temperature and normal pressure environment, putting the mixture into a clean corundum crucible, and transferring the corundum crucible with the sample into a muffle furnace;
or directly putting the mixture of barium element in the barium-containing compound, tin element in the tin-containing compound and germanium element in the germanium-containing compound in the ratio of 0.75-1.45:0.6-1.4:0.7-1.3 or the mixture of the barium-containing compound, the tin-containing compound, the germanium-containing compound and the fluxing agent into a clean corundum crucible, grinding for multiple times and then sintering for standby;
b. c, placing the sample ground and prepared in the step a into a muffle furnace, heating from room temperature to 400-700 ℃ at a speed of 5-10 ℃/min at a low temperature stage, preserving heat for 10-20 hours, heating to 1000-1700 ℃ at a temperature of 1-5 ℃/min, and preserving heat for 30-100 hours;
c. cooling to room temperature at the speed of 0.5-10 ℃/h, taking out the sample, detecting and identifying the sample by an X-ray single crystal diffractometer, and confirming to prepare the barium-tin-germanic acid crystal.
7. The method of claim 5, wherein the top seed pulling method is performed by:
a. heating the single-phase polycrystalline powder of the compound barium tin germanium acid obtained in any one of claims 1-3 or the mixture of the single-phase polycrystalline powder of the compound barium tin germanium acid obtained in any one of claims 1-3 and a fluxing agent to melt to obtain mixed melt, and cooling or growing at constant temperature to prepare a compound barium tin germanium acid crystal;
or directly heating the mixture of barium in the barium-containing compound, tin in the tin-containing compound and germanium in the germanium-containing compound in the ratio of 0.75-1.45:0.6-1.4:0.7-1.3 or the mixture of the barium-containing compound, the tin-containing compound, the germanium-containing compound and the fluxing agent to melt to obtain a mixed solution, and cooling or growing at constant temperature to prepare the barium-tin-germanium acid crystal.
b. Preparing barium tin germanic acid seed crystal: slowly cooling the mixed solution obtained in the step a to room temperature at a speed of 0.5-10 ℃/h, and spontaneously crystallizing to obtain barium-tin-germanium acid seed crystal;
c. c, placing the crucible containing the mixed solution prepared in the step a into a crystal growth furnace, fixing the seed crystal obtained in the step b on a seed rod, preheating the seed crystal for 5-100 minutes, lowering the seed crystal to be in contact with the liquid surface of the mixed solution or the mixed solution for remelting, keeping the temperature for 5-60 minutes, and lowering the temperature to the saturation temperature at a speed of 0.1-10 ℃/h.
d. Then slowly cooling at the speed of 0.1-5 ℃/day, and rotating a seed rod or a rotating crucible at the rotating speed of 0-60 rpm to perform crystal growth; after the monocrystal grows to the required size, the crystal is lifted off the surface of the mixed molten liquid, cooled to room temperature at the speed of 1-80 ℃/h, and then taken out of a hearth, thus obtaining the barium-tin-germanium acid nonlinear optical crystal.
8. The method of claim 7, wherein the molar ratio of the single-phase polycrystalline powder of the compound barium-tin-germanium acid or the single-phase polycrystalline powder of the compound barium-tin-germanium acid to the fluxing agent is 1:0.1-30; or wherein the molar ratio of the barium-containing compound, the tin-containing compound, and the germanium-containing compound to the fluxing agent is 1:1:1:0.1-30; wherein the single fluxing agent comprises H 3 BO 3 、B 2 O 3 、Bi 2 O 3 、PbO、PbF 2 、MoO 3 、NaF、SnF 2 、BaF 2 、GeF 4 、KF、LiF、K 2 CO 3 、Na 2 CO 3 、Li 2 CO 3 、GeO 2 One or more of these, the composite fluxing agent comprising H 3 BO 3 -NaF、H 3 BO 3 -PbO、H 3 BO 3 -PbF 2 、H 3 BO 3 -MoO 3 、H 3 BO 3 -SnF 2 、H 3 BO 3 -BaF 2 、H 3 BO 3 -GeF 4 、H 3 BO 3 -KF、H 3 BO 3 -LiF、H 3 BO 3 -K 2 CO 3 、H 3 BO 3 -Na 2 CO 3 、H 3 BO 3 -Li 2 CO 3 、PbO-PbF 2 、SnF 2 -GeO 2 、H 3 BO 3 -Bi 2 O 3 -NaF、H 3 BO 3 -PbO-PbF 2 、BaF 2 -SnF 2 -Bi 2 O 3 、BaF 2 -Bi 2 O 3 -MoO 3 、PbO-SnF 2 -MoO 3 、KF-H 3 BO 3 -PbF 2 One or more of the following.
9. The method according to claim 8, wherein the composite flux H 3 BO 3 H in the NaF System 3 BO 3 The molar ratio of the catalyst to NaF is 1-10:2-5; h 3 BO 3 H in PbO System 3 BO 3 The mol ratio of the catalyst to PbO is 1-10:1-4; h 3 BO 3 -PbF 2 H in the system 3 BO 3 With PbF 2 The molar ratio is 1-10:1-5; h 3 BO 3 -MoO 3 H in the system 3 BO 3 With MoO 3 The molar ratio is 1-10:2-8; h 3 BO 3 -SnF 2 H in the system 3 BO 3 With SnF 2 The molar ratio of (2) is 1-10:1-6; h 3 BO 3 -BaF 2 H in the system 3 BO 3 With BaF 2 The molar ratio of (2) is 1-10:1-3; h 3 BO 3 -GeF 4 H in the system 3 BO 3 With GeF 4 The molar ratio of (2) is 1-10:1-3.5; h 3 BO 3 H in-KF System 3 BO 3 And K is equal toThe molar ratio of F is 1-10:1-5; h 3 BO 3 H in LiF System 3 BO 3 The molar ratio of LiF to LiF is 1-10:0.5-4; h 3 BO 3 -K 2 CO 3 H in the system 3 BO 3 And K is equal to 2 CO 3 The molar ratio is 1-10:1-4.5; h 3 BO 3 -Na 2 CO 3 H in the system 3 BO 3 With Na and Na 2 CO 3 The molar ratio is 1-10:0.5-2.5; h 3 BO 3 -Li 2 CO 3 H in the system 3 BO 3 With Li 2 CO 3 The molar ratio is 1-10:2-5; pbO-PbF 2 PbO and PbF in the system 2 The molar ratio is 1-4:1-5; snF (SnF) 2 -GeO 2 SnF in System 2 With GeO 2 The molar ratio is 1-6:0.5-3; h 3 BO 3 -Bi 2 O 3 H in the NaF System 3 BO 3 、Bi 2 O 3 The molar ratio of the catalyst to NaF is 1-10:1-4:2-5; h 3 BO 3 -PbO-PbF 2 H in the system 3 BO 3 PbO and PbF 2 The molar ratio is 1-10:1-4:1-5; baF (Baf) 2 -SnF 2 -Bi 2 O 3 BaF in System 2 、SnF 2 With Bi 2 O 3 The molar ratio is 1-3:1-6:1-4; baF (Baf) 2 -Bi 2 O 3 -MoO 3 BaF in System 2 、Bi 2 O 3 With MoO 3 The molar ratio is 1-3:1-4:2-8; pbO-SnF 2 -MoO 3 PbO and SnF in the system 2 With MoO 3 The molar ratio is 1-4:1-6:2-8; KF-H 3 BO 3 -PbF 2 KF, H in the system 3 BO 3 With PbF 2 The molar ratio is 1-5:1-10:1-5.
10. The use of the barium-tin-germanium acid nonlinear optical crystal according to claim 4, wherein the barium-tin-germanium acid nonlinear optical crystal is widely applied to optical devices in the fields of frequency doubling generators, upper or lower frequency converters, optical parametric oscillators, ferroelectrics, piezoelectrics, pyroelectric and the like.
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