CN114635178B - Compound low Wen Xiangjiu strontium lithium borate and low Wen Xiangjiu strontium lithium borate nonlinear optical crystal, preparation method and application - Google Patents
Compound low Wen Xiangjiu strontium lithium borate and low Wen Xiangjiu strontium lithium borate nonlinear optical crystal, preparation method and application Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 241
- 150000001875 compounds Chemical class 0.000 title claims abstract description 175
- 230000003287 optical effect Effects 0.000 title claims abstract description 92
- YESJICRDVJRZLA-UHFFFAOYSA-N lithium strontium borate Chemical compound [Li+].[Sr++].[O-]B([O-])[O-] YESJICRDVJRZLA-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 89
- 238000009461 vacuum packaging Methods 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000000155 melt Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 82
- 238000010438 heat treatment Methods 0.000 claims description 53
- 238000001816 cooling Methods 0.000 claims description 51
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 46
- 238000002156 mixing Methods 0.000 claims description 41
- 229910052697 platinum Inorganic materials 0.000 claims description 41
- 239000000843 powder Substances 0.000 claims description 39
- 239000011259 mixed solution Substances 0.000 claims description 30
- 238000007789 sealing Methods 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000010453 quartz Substances 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 238000011068 loading method Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 229910013553 LiNO Inorganic materials 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 12
- 229910003514 Sr(OH) Inorganic materials 0.000 claims description 12
- 229910013184 LiBO Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000004080 punching Methods 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- -1 strontium lithium nonaborate Chemical compound 0.000 abstract description 8
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 4
- 238000005538 encapsulation Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract 1
- 238000003746 solid phase reaction Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000006184 cosolvent Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 2
- ZYPDJSJJXZWZJJ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-piperidin-4-yloxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OC1CCNCC1 ZYPDJSJJXZWZJJ-UHFFFAOYSA-N 0.000 description 2
- HYINOYREDQVZPQ-UHFFFAOYSA-N B([O-])([O-])[O-].[Ba+2].[Cs+] Chemical compound B([O-])([O-])[O-].[Ba+2].[Cs+] HYINOYREDQVZPQ-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- HHCLNZBCCQDVOQ-UHFFFAOYSA-N 1-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]pyrazol-3-yl]methyl]piperazin-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(N1CC2=C(CC1)NN=N2)=O)CN1C(CNCC1)=O HHCLNZBCCQDVOQ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910006715 Li—O Inorganic materials 0.000 description 1
- OUPMOMCMVXZDFV-UHFFFAOYSA-N [Cd+2].B([O-])([O-])[O-].[Sr+2] Chemical compound [Cd+2].B([O-])([O-])[O-].[Sr+2] OUPMOMCMVXZDFV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
Classifications
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/128—Borates 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
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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
- C30B17/00—Single-crystal growth onto a seed which remains in the melt during growth, e.g. Nacken-Kyropoulos method
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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- 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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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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Abstract
The invention provides a compound low Wen Xiangjiu strontium lithium borate and strontium lithium nonaborate nonlinear optical crystal, a preparation method and application thereof, wherein the chemical formula of the compound is LiSrB 9 O 15 The molecular weight is 431.85, and the polymer is prepared by adopting a solid phase synthesis method or a vacuum encapsulation method; the chemical formula of the crystal is LiSrB 9 O 15 Molecular weight is 431.85, which belongs to orthorhombic system, and space group isP2 1 2 1 2 1 The unit cell parameters area=8.5432(5)Å，b=8.6390(4)Å，c=14.8622(8)Å，α=β=γ=90°, unit cell volume 1096.90 (10) a 3 The frequency doubling effect of the crystal is about KH 2 PO 4 The ultraviolet cut-off edge of 0.5 times (KDP) is shorter than 240nm, and the crystal has good chemical stability by adopting a melt method, a high Wen Rongye method, a vacuum packaging method or a hydrothermal method, and can be used as an ultraviolet nonlinear optical crystal to be applied to an all-solid-state laser.
Description
Technical Field
The invention relates to a low Wen Xiangjiu lithium strontium borate LiSrB compound 9 O 15 And low Wen Xiangjiu lithium strontium borate LiSrB 9 O 15 Nonlinear optical crystal, preparation method and application thereof.
Background
Metal borates are widely synthesized and reported due to their abundant structure and excellent properties. Due to the diversity of structures from isolated planar triangles [ BO 3 ]And tetrahedron [ BO ] 4 ]The metal borate nonlinear optical materials are always hot points of research because of the wide transparent range, good chemical and thermal stability and large laser damage threshold value of the metal borate crystals from the group to the group of the metal borate crystals which are aggregated into zero-dimensional clusters, one-dimensional infinite chains, two-dimensional layered structures and three-dimensional frames. The boron atom being bound to an oxygen atom to form [ BO ] 2 ]Linear rod, [ BO ] 3 ]Plane triangle and [ BO ] 4 ]Coordination tetrahedral combination. In addition, many borates can exhibit great flexibility in their crystal structure under the control of large radius metal cations to build polymorphic structure types, [ B ] 3 O 7 ]The six-membered ring consists of two [ BO ] 3 ]Triangle and one [ BO ] 4 ]Tetrahedral composition. And [ B ] 3 O 6 ]Ring comparison, [ B ] 3 O 7 ]The rings have a variety of attachment means that can form a three-dimensional framework. In this three-dimensional framework, all of the oxygen is bridging oxygen, which will eliminate non-bonded electrons or dangling bonds of oxygen. Thus, with [ B ] 3 O 7 ]The borate of the ring can make the cut-off edge blue shift to increase the forbidden bandwidth, and under the regulation and control action of large-radius metal cations, the method is characterized by that [ B 3 O 7 ]Borates of three-dimensional framework structures formed by the groups have higher structural flexibility. Alkali metal elements of smaller radius and divalent metal elements of larger radius are filled into tunnels formed through the B-O skeleton, e.g. AMB 9 O 15 (a=li, na; m=ba, sr, pb) and the like.
In the previous research, the invention discloses a high-low temperature phase strontium cadmium borate crystal, a preparation method and application (patent application)201410735826.2), sodium potassium barium boron oxide and sodium potassium barium boron oxide optical crystals, preparation methods and applications (patent application No. 201510026660.1), lithium cesium heptaborate nonlinear optical crystals, preparation methods and applications (patent application No. 201510052379.5), barium cesium borate and barium cesium borate nonlinear optical crystals, preparation methods and applications (patent application No. 20151094637. X), lithium strontium borate nonlinear optical crystals, preparation methods and applications (patent application No. 201310345567.8) and other related patents. The main difference between the present invention and the above patent is that the low Wen Xiangjiu lithium strontium borate LiSrB 9 O 15 In [ B ] 3 O 7 ]Is a basic building unit, and forms a complex three-dimensional network structure by sharing oxygen atoms at the top points. The three-dimensional network structure constructs two pore channels, and Li and Sr atoms are respectively filled in the two pore channels. Li and Sr ions are connected with the boron-oxygen anion frame through Li-O and Sr-O ion bonds, the bonding acting forces of the structures are different, the structures and the growth habits are completely different, and the low Wen Xiangjiu lithium strontium borate LiSrB 9 O 15 The crystal growth method can be used for growing in a closed system or in an open system, and key parameters and crystal performances of the growth process are different from those of the first three crystals.
Disclosure of Invention
The invention aims at providing a low-temperature phase of a compound lithium strontium nonaborate, wherein the chemical formula of the compound is LiSrB 9 O 15 The molecular weight is 431.85, and the polymer is prepared by adopting a solid phase reaction method or a vacuum packaging method.
Another object of the present invention is to provide low temperature Xiang Jiu lithium strontium borate LiSrB 9 O 15 Nonlinear optical crystal of the chemical formula LiSrB 9 O 15 The molecular weight is 431.85. The crystal structure belongs to an orthorhombic system, and the space group is P2 1 2 1 2 1 The unit cell parameters areα=β=γ=90° unit cell volume +.>
It is still another object of the present invention to provide a low temperature Xiang Jiu lithium strontium borate LiSrB 9 O 15 The preparation method of the nonlinear optical crystal adopts a melt method, a high Wen Rongye method, a vacuum packaging method, a hydrothermal method or a room temperature solution method to grow the crystal.
It is a further object of the present invention to provide low temperature Xiang Jiu lithium strontium borate LiSrB 9 O 15 Use of a nonlinear optical crystal.
The chemical formula of the compound is LiSrB, and the compound is low in Wen Xiangjiu lithium strontium borate 9 O 15 The molecular weight is 431.85, and the polymer is prepared by adopting a solid phase synthesis method or a vacuum encapsulation method.
The preparation method of the low Wen Xiangjiu lithium strontium borate compound adopts a solid phase synthesis method or a vacuum encapsulation method, and comprises the following specific operations:
the solid phase synthesis method is used for preparing low Wen Xiangjiu lithium strontium borate:
mixing Li-containing compound, sr-containing compound and B-containing compound uniformly according to a molar ratio of 1:1:9, loading into a platinum crucible, heating to 450-760 ℃ in a muffle furnace, and keeping the temperature for 24-120 hours to obtain the compound LiSrB 9 O 15 The Li-containing compound is LiF, liBO 2 、LiOH、Li 2 CO 3 、LiNO 3 、LiHCO 3 Or LiBF 4 The method comprises the steps of carrying out a first treatment on the surface of the The Sr-containing compound is SrF 2 、Sr(OH) 2 、SrCO 3 、Sr(NO 3 ) 2 、Sr(HCO 3 ) 2 Or Sr (BF 4 ) 2 The compound containing B is H 3 BO 3 Or B is a 2 O 3 ；
The vacuum packaging method is used for preparing low Wen Xiangjiu lithium strontium borate:
mixing Li-containing compound, sr-containing compound and B-containing compound at a molar ratio of 1:1:9, placing into quartz tube, vacuumizing the quartz tube to vacuum degree of 1×10 -3 Pa, sealing at high temperature, placing in a muffle furnace, heating to 450-760 deg.C at a rate of 5-10deg.C/h, and keeping constant temperature for 24-120 hr to obtain compound LiSrB 9 O 15 The Li-containing compound is LiF、LiBO 2 、LiOH、Li 2 CO 3 、LiNO 3 、LiHCO 3 Or LiBF 4 The method comprises the steps of carrying out a first treatment on the surface of the The Sr-containing compound is SrF 2 、Sr(OH) 2 、SrCO 3 、Sr(NO 3 ) 2 、Sr(HCO 3 ) 2 Or Sr (BF 4 ) 2 The compound containing B is H 3 BO 3 Or B is a 2 O 3 。
Low-temperature Xiang Jiu lithium strontium borate nonlinear optical crystal with chemical formula of LiSrB 9 O 15 Molecular weight is 431.85, belongs to orthorhombic system, and space group is P2 1 2 1 2 1 The unit cell parameters are α=β=γ=90°, unit cell volume +.>
The preparation method of the low Wen Xiangjiu lithium strontium borate nonlinear optical crystal adopts a melt method, a high Wen Rongye method, a vacuum packaging method, a hydrothermal method or a room temperature solution method to grow the crystal;
the specific operation of growing the low-temperature Xiang Jiu lithium strontium borate nonlinear optical crystal by the melt method is carried out according to the following steps:
a. mixing Li-containing compound, sr-containing compound and B-containing compound uniformly according to a molar ratio of 1:1:9, loading into a platinum crucible, heating to 500-650 ℃ in a muffle furnace, and keeping the temperature for 24-120 hours to obtain the compound LiSrB 9 O 15 Polycrystalline powder of LiF and LiBO as Li-containing compound 2 、LiOH、Li 2 CO 3 、LiNO 3 、LiHCO 3 Or LiBF 4 The method comprises the steps of carrying out a first treatment on the surface of the The Sr-containing compound is SrF 2 、Sr(OH) 2 、SrCO 3 、Sr(NO 3 ) 2 、Sr(HCO 3 ) 2 Or Sr (BF 4 ) 2 The compound containing B is H 3 BO 3 Or B is a 2 O 3 ；
b. C, preparing a compound LiSrB obtained in the step a 9 O 15 Placing the polycrystalline powder into a platinum crucible, placing the crucible in a muffle furnace, heating to 650-850 ℃, and keeping the temperature for 10-120 hours to obtain a mixed melt;
c. slowly cooling the mixed melt obtained in the step b to 450 ℃ at the speed of 0.1-2 ℃/h, and rapidly cooling to room temperature at the speed of 5-10 ℃/h to obtain LiSrB 9 O 15 Seed crystal;
d. crystal growth in a compound melt using the Czochralski method: c, fixing the seed crystal obtained in the step c on a seed rod, applying 2-20rpm crystal rotation from the upper side of the mixed melt obtained in the step b through a crystal growth controller, lifting the seed crystal at the speed of 1-10 mm/day, simultaneously cooling to 600-840 ℃ at the speed of 0.1-10 ℃/h, and obtaining LiSrB after the crystal growth is stopped 9 O 15 A nonlinear optical crystal;
or growing crystals in a compound melt by a kyropoulos method: c, fixing the seed crystal obtained in the step c on a seed rod, dropping the seed crystal from the upper part of the melt prepared in the step b, cooling to 600-840 ℃ at the speed of 0.1-10 ℃/h, enabling the crystal to grow for 5-15 hours, slowly lifting the crystal but not separating from the liquid surface for continuous growth, repeating the steps, and obtaining LiSrB after the crystal growth is stopped 9 O 15 A nonlinear optical crystal;
or growing crystals in the compound melt by the crucible descent method: placing the seed crystal prepared in the step c at the bottom of a crucible, and then placing the compound LiSrB prepared in the step a 9 O 15 Placing the polycrystal into a crucible, sealing the platinum crucible, placing the crucible in a growth furnace, raising the temperature of the growth furnace to 650-850 ℃, keeping the temperature constant for 10-120 hours, adjusting the position of the crucible to enable seed crystals to be micro-melted, lowering the crucible at the speed of 1-10 mm/day, simultaneously keeping the growth temperature unchanged or lowering the temperature at the cooling rate of 3 ℃/h at the maximum speed to 600-840 ℃, and quickly lowering the temperature to the room temperature at the speed of 5-10 ℃/h after the growth is finished, thus obtaining LiSrB 9 O 15 A nonlinear optical crystal;
the specific operation of growing the low-temperature Xiang Jiu lithium strontium borate nonlinear optical crystal by the high-temperature melt method is carried out according to the following steps:
a. mixing Li-containing compound, sr-containing compound and B-containing compound uniformly according to a molar ratio of 1:1:9, loading into a platinum crucible, heating to 650-850 ℃ in a muffle furnace, and keeping the temperature for 24-120 hours to obtain the compound LiSrB 9 O 15 Polycrystalline powder of LiF and LiBO as Li-containing compound 2 、LiOH、Li 2 CO 3 、LiNO 3 、LiHCO 3 Or LiBF 4 The method comprises the steps of carrying out a first treatment on the surface of the The Sr-containing compound is SrF 2 、Sr(OH) 2 、SrCO 3 、Sr(NO 3 ) 2 、Sr(HCO 3 ) 2 Or Sr (BF 4 ) 2 The compound containing B is H 3 BO 3 Or B is a 2 O 3 ；
b. C, preparing a compound LiSrB obtained in the step a 9 O 15 Uniformly mixing polycrystalline powder and fluxing agent according to a molar ratio of 1:0.1-6, then charging into a platinum crucible, heating to 650-850 ℃, and keeping the temperature for 5-120 hours to obtain mixed solution, wherein the cosolvent is H 3 BO 3 ，B 2 O 3 PbO or PbF 2 ；
c. Preparing seed crystals: c, placing the mixed solution obtained in the step b into a single crystal furnace, slowly reducing the temperature to 550 ℃ at the speed of 0.1-2 ℃/h, and rapidly reducing the temperature to room temperature at the speed of 5-10 ℃/h to obtain LiSrB 9 O 15 Seed crystal;
d. growing a crystal: c, fixing the seed crystal obtained in the step c on a seed rod, applying 2-20rpm crystal rotation from the upper side of the mixed solution obtained in the step b through a crystal growth controller, cooling to 600-840 ℃ at a speed of 0.1-3 ℃/h, and obtaining LiSrB after crystal growth is stopped 9 O 15 A nonlinear optical crystal;
the specific operation of growing the low-temperature Xiang Jiu lithium strontium borate nonlinear optical crystal by the vacuum packaging method is carried out according to the following steps:
a. uniformly mixing a Li-containing compound, a Sr-containing compound and a B-containing compound according to a molar ratio of 1:1:9, placing the mixture in a muffle furnace, heating to 600-850 ℃, and keeping the temperature for 24-120 hours to obtain the compound LiSrB 9 O 15 Polycrystalline powder of LiF and LiBO as Li-containing compound 2 、LiOH、Li 2 CO 3 、LiNO 3 、LiHCO 3 Or LiBF 4 The method comprises the steps of carrying out a first treatment on the surface of the The Sr-containing compound is SrF 2 、Sr(OH) 2 、SrCO 3 、Sr(NO 3 ) 2 、Sr(HCO 3 ) 2 Or Sr (BF 4 ) 2 The compound containing B is H 3 BO 3 Or B is a 2 O 3 ；
b. C, preparing a compound LiSrB obtained in the step a 9 O 15 Uniformly mixing polycrystalline powder and fluxing agent according to a molar ratio of 1:0.1-6, filling into a quartz tube, sealing at high temperature, placing into a muffle furnace, heating to 650-800 ℃, keeping the temperature for 5-120 hours, cooling to 450 ℃ at a speed of 0.1-3 ℃/h, and rapidly cooling to room temperature at a speed of 5-10 ℃/h to obtain LiSrB 9 O 15 Nonlinear optical crystal, the cosolvent is H 3 BO 3 ，B 2 O 3 PbO or PbF 2 ；
The specific operation of growing the low-temperature Xiang Jiu lithium strontium borate nonlinear optical crystal by the hydrothermal method is carried out according to the following steps:
a. mixing Li-containing compound, sr-containing compound and B-containing compound uniformly according to a molar ratio of 1:1:9, loading into a platinum crucible, heating to 500-650 ℃ in a muffle furnace, and keeping the temperature for 24-120 hours to obtain the compound LiSrB 9 O 15 Polycrystalline powder of LiF and LiBO as Li-containing compound 2 、LiOH、Li 2 CO 3 、LiNO 3 、LiHCO 3 Or LiBF 4 The method comprises the steps of carrying out a first treatment on the surface of the The Sr-containing compound is SrF 2 、Sr(OH) 2 、SrCO 3 、Sr(NO 3 ) 2 、Sr(HCO 3 ) 2 Or Sr (BF 4 ) 2 The compound containing B is H 3 BO 3 Or B is a 2 O 3 ；
b. C, preparing a compound LiSrB obtained in the step a 9 O 15 Dissolving the polycrystalline powder in 20-100mL deionized water, ultrasonic treating the incompletely dissolved mixture at 60deg.C to obtain a fully mixed solution, dissolving with LiOH and Sr (OH) 2 Adjusting the pH value to 8-11;
c. transferring the mixed solution obtained in the step b into a clean and pollution-free lining of a high-pressure reaction kettle with the volume of 100mL, and screwing and sealing the reaction kettle;
d. placing the high-pressure reaction kettle in a constant temperature box, heating to 150-350 ℃, keeping the temperature for 5-8 days, and cooling to room temperature at a cooling rate of 5-20 ℃/day to obtain LiSrB 9 O 15 A nonlinear optical crystal;
the specific operation of growing the low-temperature Xiang Jiu lithium strontium borate nonlinear optical crystal by the room-temperature solution method is carried out according to the following steps:
a. mixing Li-containing compound, sr-containing compound and B-containing compound uniformly according to a molar ratio of 1:1:9, loading into a platinum crucible, heating to 450-760 ℃ in a muffle furnace, and keeping the temperature for 24-120 hours to obtain the compound LiSrB 9 O 15 The Li-containing compound is LiF, liBO 2 、LiOH、Li 2 CO 3 、LiNO 3 、LiHCO 3 Or LiBF 4 The method comprises the steps of carrying out a first treatment on the surface of the The Sr-containing compound is SrF 2 、Sr(OH) 2 、SrCO 3 、Sr(NO 3 ) 2 、Sr(HCO 3 ) 2 Or Sr (BF 4 ) 2 The compound containing B is H 3 BO 3 Or B is a 2 O 3 ；
b. C, preparing a compound LiSrB obtained in the step a 9 O 15 Placing the polycrystalline powder into a cleaned glass container, adding 20-100mL deionized water, and performing ultrasonic treatment to dissolve, and mixing with HF, liOH and Sr (OH) 2 Adjusting pH to 8-11, and filtering with filter paper to obtain mixed solution;
c. placing the mixed solution obtained in the step b into a clean glass container, sealing with weighing paper, placing in a static environment without shaking, pollution and air convection, punching a plurality of small holes on the sealing to regulate the evaporation rate of water in the aqueous solution, and standing for 5-20 days at room temperature;
d. c, growing crystal particles on the bottom of the container until the crystal particle size is not changed obviously any more to obtain seed crystals;
e. selecting seed crystal with better quality in the step d, suspending the seed crystal in the mixed solution prepared in the step b, standing and growing for 10-30 days at room temperature,obtaining LiSrB 9 O 15 Nonlinear optical crystal.
The low Wen Xiangjiu lithium strontium borate nonlinear optical crystal is used for preparing harmonic light output of 2 times of frequency multiplication of 1064nm fundamental frequency light output by an Nd-YAG laser.
The application of the low Wen Xiangjiu lithium strontium borate nonlinear optical crystal in preparing an ultraviolet frequency doubling light output of 240-400 nm.
The low Wen Xiangjiu lithium strontium borate nonlinear optical crystal is used for preparing a frequency doubling generator, an upper or lower frequency converter or an optical parametric oscillator.
The invention relates to low Wen Xiangjiu lithium strontium borate LiSrB 9 O 15 The container used in the preparation process is a platinum crucible, an iridium crucible, a ceramic crucible, a quartz tube, a conical flask, a beaker, and a hydrothermal kettle with a polytetrafluoroethylene lining or a stainless steel lining provided with a platinum sleeve. When the container is a quartz tube, vacuum is needed before sealing, so that the quartz tube is prevented from being burst due to volatilization of raw materials in the reaction process. When the container is a conical flask or a beaker, the container is cleaned by acid, then rinsed by deionized water and dried.
The low Wen Xiangjiu lithium strontium borate LiSrB of the invention 9 O 15 The preparation method of the nonlinear optical crystal comprises the step that a resistance furnace used in the preparation process is a muffle furnace or a drying oven.
The method of the invention can obtain low Wen Xiangjiu lithium strontium borate LiSrB with the size of centimeter level 9 O 15 Nonlinear optical crystal, using large-sized crucible or container and extending crystal growth period, can obtain correspondingly large-sized nonlinear optical crystal LiSrB 9 O 15 In the LiSrB 9 O 15 The nonlinear optical crystal is easy to grow and transparent without wrapping in the growth process, and has the advantages of high growth speed, low cost, easy obtainment of large-size crystals and the like.
The preparation method of the low Wen Xiangjiu lithium strontium borate nonlinear optical crystal of the invention is adopted to obtain large-size LiSrB 9 O 15 Nonlinear optical crystal, junction according to crystalThe crystallographic data, the crystal blank is oriented, the crystal is cut according to the required angle, thickness and section size, the light-passing surface of the crystal is polished, the LiSrB can be used as a nonlinear optical device 9 O 15 The ultraviolet cut-off edge of the nonlinear optical crystal is below 240nm, and the nonlinear optical crystal has the advantages of stable physical and chemical properties, difficult deliquescence, easy processing and storage, and the like.
Drawings
FIG. 1 shows a compound LiSrB of the present invention 9 O 15 Is a powder XRD pattern of (C);
FIG. 2 shows LiSrB of the present invention 9 O 15 Structure of the crystal;
FIG. 3 is a view of LiSrB of the present invention 9 O 15 Working principle diagram of crystal-made nonlinear optical device, wherein 1 is laser, 2 is emitted light beam, 3 is LiSrB 9 O 15 The crystal, 4 is the outgoing light beam, 5 is the filter.
Detailed Description
The invention is further described below with reference to examples. It should be noted that the following examples should not be construed as limiting the scope of the invention, and any modifications made thereto do not depart from the spirit of the invention. The materials and equipment used in the present invention are commercially available unless otherwise specified.
Example 1
Preparation of the compound:
according to the reaction formula: 2LiF+2SrF 2 +10B 2 O 3 →2LiSrB 9 O 15 +BF 3 Synthesis of LiSrB compound by solid phase reaction 9 O 15 ：
The LiF and SrF are mixed according to the mol ratio of 2:2:10 2 And B 2 O 3 Mixing uniformly, loading into a platinum crucible, heating to 450 ℃ in a muffle furnace, and keeping the temperature for 24 hours to obtain the compound LiSrB 9 O 15 。
Example 2
Preparation of the compound:
according to the reaction formula: liF+SrF 2 +9H 3 BO 3 →LiSrB 9 O 15 +3HF+12H 2 O, adopting solid phase reaction method to synthesize compound LiSrB 9 O 15 ：
LiF, srF 2 ，H 3 BO 3 Uniformly mixing according to a molar ratio of 1:1:9, loading into a platinum crucible, placing into a muffle furnace, heating to 550 ℃, and keeping the temperature for 48 hours to obtain a compound LiSrB 9 O 15 。
Example 3
Preparation of the compound:
according to the reaction formula: li (Li) 2 CO 3 +2SrCO 3 +9B 2 O 3 →2LiSrB 9 O 15 +3CO 2 Synthesis of LiSrB compound by solid phase reaction 9 O 15 ：
Li is mixed with 2 CO 3 ，SrCO 3 ，B 2 O 3 Mixing uniformly according to the molar ratio of 1:2:9, loading into a platinum crucible, placing into a muffle furnace, heating to 690 ℃, and keeping the temperature for 120 hours to obtain the compound LiSrB 9 O 15 。
Example 4
Preparation of the compound:
according to the reaction formula: li (Li) 2 CO 3 +2SrCO 3 +18H 3 BO 3 →2LiSrB 9 O 15 +3CO 2 +27H 2 O, adopting solid phase reaction method to synthesize compound LiSrB 9 O 15 ：
Li is mixed with 2 CO 3 ，SrCO 3 ，B 2 O 3 Uniformly mixing according to a molar ratio of 1:2:18, loading into a platinum crucible, placing into a muffle furnace, heating to 680 ℃, and keeping the temperature for 72 hours to obtain a compound LiSrB 9 O 15 。
Example 5
Preparation of the compound:
according to the reaction formula: liOH+Sr (OH) 2 +9H 3 BO 3 →LiSrB 9 O 15 +15H 2 O, adopting solid phase reaction method to synthesize compound LiSrB 9 O 15 ：
LiOH, sr (OH) 2 ，H 3 BO 3 Uniformly mixing according to the mol ratio of 1:1:9Placing into a platinum crucible, heating to 720 deg.C in a muffle furnace, and keeping the temperature for 72 hr to obtain compound LiSrB 9 O 15 。
Example 6
Preparation of the compound:
according to the reaction formula: 2LiOH+2Sr (OH) 2 +9B 2 O 3 →2LiSrB 9 O 15 +3H 2 O, adopting solid phase reaction method to synthesize compound LiSrB 9 O 15 ：
LiOH, sr (OH) 2 ，B 2 O 3 Mixing uniformly according to the molar ratio of 2:2:9, loading into a platinum crucible, placing into a muffle furnace, heating to 650 ℃, and keeping the temperature for 100 hours to obtain the compound LiSrB 9 O 15 。
Example 7
Preparation of the compound:
according to the reaction formula: liBO 2 +SrCO 3 +8H 3 BO 3 →LiSrB 9 O 15 +12H 2 O+CO 2 Synthesis of LiSrB compound by solid phase reaction 9 O 15 ：
LiOH, srCO 3 ，H 3 BO 3 Mixing uniformly according to the molar ratio of 1:1:8, loading into a platinum crucible, placing into a muffle furnace, heating to 590 ℃, and keeping the temperature for 60 hours to obtain the compound LiSrB 9 O 15 。
Example 8
Preparation of the compound:
according to the reaction formula: liOH+SrCO 3 +9H 3 BO 3 →LiSrB 9 O 15 +14H 2 O+CO 2 Synthesis of LiSrB compound by solid phase reaction 9 O 15 ：
LiOH, sr (OH) 2 ，B 2 O 3 Uniformly mixing according to the molar ratio of 1:1:9, loading into a platinum crucible, placing into a muffle furnace, heating to 760 ℃, and keeping the temperature for 72 hours to obtain the compound LiSrB 9 O 15 。
Example 9
Preparation of the compound:
according to the reaction type：2LiNO 3 +2Sr(NO 3 ) 2 +9B 2 O 3 →2LiSrB 9 O 15 +NO 2 +O 2 Synthesis of LiSrB compound by solid phase reaction 9 O 15 ：
LiNO is to be carried out 3 ，Sr(NO 3 ) 2 ，H 3 BO 3 Uniformly mixing according to a molar ratio of 1:1:9, loading into a platinum crucible, placing into a muffle furnace, heating to 650 ℃, and keeping the temperature for 80 hours to obtain a compound LiSrB 9 O 15 。
Example 10
Preparation of the compound:
according to the reaction formula: liOH+Sr (NO) 3 ) 2 +9H 3 BO 3 →LiSrB 9 O 15 +14H 2 O+2NO 2 +O 2 Synthesis of LiSrB compound by solid phase reaction 9 O 15 ：
LiOH, sr (OH) 2 ，B 2 O 3 Uniformly mixing according to a molar ratio of 1:1:9, loading into a platinum crucible, placing into a muffle furnace, heating to 480 ℃, and keeping the temperature for 36 hours to obtain a compound LiSrB 9 O 15 。
Example 11
Preparation of the compound:
according to the reaction formula: 2LiNO 3 +2Sr(NO 3 ) 2 +9B 2 O 3 →2LiSrB 9 O 15 +NO 2 +O 2 The compound LiSrB is synthesized by adopting a vacuum packaging method 9 O 15 ：
LiNO is to be carried out 3 ，Sr(NO 3 ) 2 ，H 3 BO 3 Mixing at a molar ratio of 1:1:9, placing into quartz tube with phi 40mm, vacuumizing the quartz tube to vacuum degree of 1×10 -3 Pa, sealing at high temperature, placing in a muffle furnace, heating to 450 ℃ at a rate of 10 ℃/h, and keeping the temperature for 24 hours to obtain the compound LiSrB 9 O 15 。
Example 12
Preparation of the compound:
according to the reaction formula: 2LiF+2SrF 2 +10B 2 O 3 →2LiSrB 9 O 15 +2BF 3 The compound LiSrB is synthesized by adopting a vacuum packaging method 9 O 15 ：
LiF, srF 2 ，B 2 O 3 Mixing at a molar ratio of 2:2:9, placing into quartz tube with phi 40mm, vacuumizing the quartz tube to vacuum degree of 1×10 -3 Pa, sealing at high temperature, placing in a muffle furnace, heating to 680 deg.C at a rate of 5 deg.C/h, and keeping constant temperature for 72 hr to obtain compound LiSrB 9 O 15 。
Example 13
Preparation of the compound:
according to the reaction formula: li (Li) 2 CO 3 +2SrCO 3 +9B 2 O 3 →2LiSrB 9 O 15 +3CO 2 The compound LiSrB is synthesized by adopting a vacuum packaging method 9 O 15 ：
Li is mixed with 2 CO 3 ，SrCO 3 ，B 2 O 3 Mixing at a molar ratio of 1:2:9, placing into quartz tube with phi 40mm, vacuumizing the quartz tube to vacuum degree of 1×10 -3 Pa, sealing at high temperature, placing in a muffle furnace, heating to 550deg.C at a rate of 8deg.C/h, and keeping the temperature for 100 hr to obtain compound LiSrB 9 O 15 。
Example 14
Preparation of the compound:
according to the reaction formula: 2LiOH+2Sr (OH) 2 +9B 2 O 3 →2LiSrB 9 O 15 +3H 2 O, adopting a vacuum packaging method to synthesize a compound LiSrB 9 O 15 ：
LiOH, sr (OH) 2 ，B 2 O 3 Mixing at a molar ratio of 2:2:9, placing into quartz tube with phi 40mm, vacuumizing the quartz tube to vacuum degree of 1×10 -3 Pa, sealing at high temperature, placing in a muffle furnace, heating to 760 deg.C at a rate of 5 deg.C/h, and keeping constant for 120 hr to obtain compound LiSrB 9 O 15 。
Example 15
Growth of LiSrB by melt process 9 O 15 Nonlinear optical crystal:
LiSrB, a compound prepared according to example 1 9 O 15 Placing the polycrystalline powder into a platinum crucible, placing the platinum crucible into a muffle furnace, heating to 750 ℃, and keeping the temperature for 10 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 450 ℃ at the speed of 0.1 ℃/h, and rapidly cooling to room temperature at the speed of 5 ℃/h to obtain LiSrB 9 O 15 Seed crystal;
growing the crystal by adopting a pulling method: fixing the obtained seed crystal on a seed rod, seeding from above the prepared mixed melt, applying 2rpm crystal rotation by a crystal growth controller, lifting the seed crystal at a speed of 1 mm/day, reducing the temperature to 650 ℃ at a speed of 0.1 ℃/h, and obtaining LiSrB with the size of 18mm multiplied by 15mm multiplied by 11mm after the crystal growth is stopped 9 O 15 Nonlinear optical crystal.
Example 16
Growth of LiSrB by melt process 9 O 15 Nonlinear optical crystal:
LiSrB of the compound prepared according to example 2 9 O 15 Placing the polycrystalline powder into a platinum crucible, placing the crucible in a muffle furnace, heating to 650 ℃, and keeping the temperature for 120 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 450 ℃ at the speed of 2 ℃/h, and rapidly cooling to room temperature at the speed of 10 ℃/h to obtain LiSrB 9 O 15 Seed crystal;
growing the crystal by adopting a pulling method: fixing the obtained seed crystal on a seed rod, applying 20rpm crystal rotation from above the prepared mixed melt, lifting the seed crystal at a speed of 10 mm/day, cooling to 600deg.C at a speed of 10deg.C/h, and stopping crystal growth to obtain LiSrB with a size of 18mm×15mm×13mm 9 O 15 Nonlinear optical crystal.
Example 17
Growth of LiSrB by melt process 9 O 15 Nonlinear optical crystal:
LiSrB, a compound prepared according to example 3 9 O 15 Placing the polycrystalline powder into a platinum crucible, placing the crucible in a muffle furnace, heating to 850 ℃, and keeping the temperature for 100 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 450 ℃ at the speed of 1.5 ℃/h, and rapidly cooling to room temperature at the speed of 8 ℃/h to obtain LiSrB 9 O 15 Seed crystal;
the crystal is grown by adopting a kyropoulos method: fixing the obtained seed crystal on seed rod, lowering the temperature from above the prepared mixed melt to 840 deg.C at a rate of 0.1 deg.C/h, allowing crystal to grow for 5 hr, slowly lifting the crystal without separating from the liquid surface, and repeating the process for 3 times to obtain LiSrB with dimensions of 15mm×15mm×10mm 9 O 15 Nonlinear optical crystal.
Example 18
Growth of LiSrB by melt process 9 O 15 Nonlinear optical crystal:
LiSrB, a compound prepared according to example 4 9 O 15 Placing the polycrystalline powder into a platinum crucible, placing the platinum crucible into a muffle furnace, heating to 700 ℃, and keeping the temperature for 24 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 450 ℃ at the speed of 2 ℃/h, and rapidly cooling to room temperature at the speed of 6 ℃/h to obtain LiSrB 9 O 15 Seed crystal;
the crystal is grown by adopting a kyropoulos method: fixing the obtained seed crystal on seed rod, lowering the temperature of the seed crystal from above the mixed melt to 680 deg.C at a rate of 10deg.C/h, allowing crystal to grow for 15 hr, slowly lifting the crystal without separating from the liquid surface, and repeating the process for 3 times to obtain LiSrB with size of 20mm×19mm×16mm 9 O 15 Nonlinear optical crystal.
Example 19
Growth of LiSrB by melt process 9 O 15 Nonlinear optical crystal:
LiSrB, a compound prepared according to example 5 9 O 15 Placing the polycrystalline powder into a platinum crucible, heating to 780 ℃, and keeping the temperature for 10 hours to obtain a mixed melt;
mixing the obtained mixtureSlowly cooling the melt at a rate of 2 ℃/h to 450 ℃, and rapidly cooling to room temperature at a rate of 5 ℃/h to obtain LiSrB 9 O 15 Seed crystal;
growing crystals in a compound melt by a crucible descent method: the seed crystal obtained was placed in the bottom of a crucible, and then the compound LiSrB prepared in example 5 was placed 9 O 15 Placing polycrystalline powder into crucible, sealing platinum crucible, heating growth furnace to 650 deg.C, holding temperature for 10 hr, regulating crucible position to make seed crystal micro-melt, reducing crucible at 1 mm/day, reducing crucible at 3 deg.C/h to 600 deg.C, after growth is completed, quickly reducing temperature to room temperature at 10 deg.C/h to obtain LiSrB with size of 16mm×15mm×13mm 9 O 15 Nonlinear optical crystal.
Example 20
Growth of LiSrB by melt process 9 O 15 Nonlinear optical crystal:
LiSrB of the compound prepared according to example 6 9 O 15 Placing the polycrystalline powder into a platinum crucible, heating to 850 ℃, and keeping the temperature for 120 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 450 ℃ at the speed of 1.5 ℃/h, and rapidly cooling to room temperature at the speed of 10 ℃/h to obtain LiSrB 9 O 15 Seed crystal;
growing crystals in a compound melt by a crucible descent method: the seed crystal obtained was placed in the bottom of a crucible, and then the compound LiSrB prepared in example 6 was placed 9 O 15 Placing polycrystalline powder into crucible, sealing platinum crucible, heating growth furnace to 850 deg.C, holding temperature for 120 hr, regulating crucible position to make seed crystal micro-melt, reducing crucible at 10 mm/day, maintaining growth temperature, quickly cooling to room temperature at 10 deg.C/hr after growth is completed to obtain LiSrB with size of 13mm×10mm×9mm 9 O 15 Nonlinear optical crystal.
Example 21
LiSrB growth by high-temperature melt method 9 O 15 Nonlinear optical crystal:
LiSrB of the compound prepared according to example 7 9 O 15 Polycrystalline powder and flux B 2 O 3 Uniformly mixing according to a molar ratio of 1:0.1, loading into a platinum crucible, heating to 650 ℃, and keeping the temperature for 5 hours to obtain mixed melt;
preparing seed crystals: the obtained mixed solution is placed in a single crystal furnace, slowly cooled to 550 ℃ at the speed of 0.1 ℃/h, and then rapidly cooled to room temperature at the speed of 5 ℃/h, thus obtaining LiSrB 9 O 15 Seed crystal;
growing a crystal: fixing the obtained seed crystal on a seed rod, seeding from the upper part of the mixed solution, applying 2rpm crystal rotation by a crystal growth controller, cooling to 600 ℃ at the rate of 0.1 ℃/h, and obtaining LiSrB with the size of 18mm multiplied by 15mm multiplied by 14mm after the crystal growth is stopped 9 O 15 Nonlinear optical crystal.
Example 22
LiSrB growth by high-temperature melt method 9 O 15 Nonlinear optical crystal:
the compound LiSrB prepared according to example 8 9 O 15 Polycrystalline powder and flux H 3 BO 3 Uniformly mixing according to a molar ratio of 1:6, loading into a platinum crucible, heating to 730 ℃, and keeping the temperature for 52 hours to obtain mixed melt;
preparing seed crystals: the obtained mixed solution is placed in a single crystal furnace, slowly cooled to 550 ℃ at the speed of 1 ℃/h, and then rapidly cooled to room temperature at the speed of 8 ℃/h, thus obtaining LiSrB 9 O 15 Seed crystal;
growing a crystal: fixing the obtained seed crystal on a seed rod, seeding from the upper part of the mixed solution, applying 10rpm crystal rotation by a crystal growth controller, cooling to 700 ℃ at a speed of 1 ℃/h, and stopping crystal growth to obtain LiSrB with the size of 14mm multiplied by 12mm multiplied by 10mm 9 O 15 Nonlinear optical crystal.
Example 23
LiSrB growth by high-temperature melt method 9 O 15 Nonlinear optical crystal:
the compound LiSrB prepared according to example 9 9 O 15 Uniformly mixing polycrystalline powder and a fluxing agent PbO according to a molar ratio of 1:4, placing the mixture into a platinum crucible, heating the mixture to 850 ℃, and keeping the temperature for 5 hours to obtain a mixed solution;
preparing seed crystals: the obtained mixed solution is placed in a single crystal furnace, slowly cooled to 550 ℃ at the speed of 1.5 ℃/h, and then rapidly cooled to room temperature at the speed of 10 ℃/h, thus obtaining LiSrB 9 O 15 Seed crystal;
growing a crystal: fixing the obtained seed crystal on a seed rod, seeding from above the mixed solution, applying 10rpm crystal rotation by a crystal growth controller, cooling to 840 deg.C at 2 deg.C/h, and stopping crystal growth to obtain LiSrB with size of 15mm×15mm×10mm 9 O 15 Nonlinear optical crystal.
Example 24
LiSrB growth by high-temperature melt method 9 O 15 Nonlinear optical crystal:
the compound LiSrB prepared according to example 10 9 O 15 Polycrystalline powder and fluxing agent PbF 2 Uniformly mixing according to a molar ratio of 1:3, then filling the mixture into a platinum crucible, heating to 800 ℃, and keeping the temperature for 120 hours to obtain mixed melt;
preparing seed crystals: the obtained mixed solution is placed in a single crystal furnace, slowly cooled to 550 ℃ at the speed of 3 ℃/h, and then rapidly cooled to room temperature at the speed of 10 ℃/h, thus obtaining LiSrB 9 O 15 Seed crystal;
growing a crystal: fixing the obtained seed crystal on a seed rod, seeding from the upper part of the mixed solution, applying 15rpm crystal rotation by a crystal growth controller, cooling to 780 ℃ at the speed of 0.2 ℃/h, and obtaining LiSrB with the size of 20mm multiplied by 19mm multiplied by 16mm after the crystal growth is stopped 9 O 15 Nonlinear optical crystal.
Example 25
Vacuum packaging method for growing LiSrB 9 O 15 Nonlinear optical crystal:
the compound LiSrB prepared according to example 11 9 O 15 Polycrystalline powder and flux H 3 BO 3 Mixing at a molar ratio of 1:0.1, placing into quartz tube with phi 40mm, vacuumizing the quartz tube to vacuum degree of 1×10 -3 Pa, sealing at high temperature, placing in a muffle furnace, heating to 650deg.C, keeping constant temperature for 5 hr, cooling to 450deg.C at rate of 0.1deg.C/h, and rapidly cooling to room temperature at rate of 8deg.C/h to obtain LiSrB with dimensions of 4mm×4mm×2mm 9 O 15 Nonlinear optical crystal.
Example 26
Vacuum packaging method for growing LiSrB 9 O 15 Nonlinear optical crystal:
the compound LiSrB prepared according to example 12 9 O 15 Polycrystalline powder and cosolvent H 3 BO 3 Mixing at a molar ratio of 1:6, placing into quartz tube with phi 40mm, vacuumizing the quartz tube to vacuum degree of 1×10 -3 Pa, sealing at high temperature, placing in a muffle furnace, heating to 750deg.C, keeping constant temperature for 50 hr, cooling to 450deg.C at the rate of 2deg.C/h, and rapidly cooling to room temperature at the rate of 10deg.C/h to obtain LiSrB with dimensions of 3mm×3mm×2mm 9 O 15 Nonlinear optical crystal.
Example 27
Vacuum packaging method for growing LiSrB 9 O 15 Nonlinear optical crystal:
the compound LiSrB prepared according to example 13 9 O 15 Polycrystalline powder and cosolvent B 2 O 3 Mixing at a molar ratio of 1:1, placing into quartz tube with phi 40mm, vacuumizing the quartz tube to vacuum degree of 1×10 -3 Pa, sealing at high temperature, placing in a muffle furnace, heating to 705 ℃, keeping the temperature for 120 hours, cooling to 450 ℃ at the speed of 3 ℃/h, and rapidly cooling to room temperature at the speed of 8 ℃/h to obtain LiSrB with the size of 4mm multiplied by 3mm multiplied by 2mm 9 O 15 Nonlinear optical crystal.
Example 28
Vacuum packaging method for growing LiSrB 9 O 15 Nonlinear optical crystal:
the compound LiSrB prepared according to example 14 9 O 15 Polycrystalline powder and cosolvent PbOMixing at a molar ratio of 1:2, placing into quartz tube with phi 40mm, vacuumizing the quartz tube to vacuum degree of 1×10 -3 Pa, sealing at high temperature, placing in a muffle furnace, heating to 800 deg.C, keeping constant temperature for 48 hr, cooling to 450 deg.C at 1.5 deg.C/h, and rapidly cooling to room temperature at 5 deg.C/h to obtain LiSrB with dimensions of 5mm×3mm×2mm 9 O 15 Nonlinear optical crystal.
Example 29
Vacuum packaging method for growing LiSrB 9 O 15 Nonlinear optical crystal:
the compound LiSrB prepared according to example 10 9 O 15 Polycrystalline powder and cosolvent PbF 2 Mixing at a molar ratio of 1:4, placing into quartz tube with phi 40mm, vacuumizing the quartz tube to vacuum degree of 1×10 -3 Pa, sealing at high temperature, placing in a muffle furnace, heating to 780 ℃, keeping the temperature for 96 hours, cooling to 450 ℃ at the speed of 0.2 ℃/h, and rapidly cooling to room temperature at the speed of 6 ℃/h to obtain LiSrB with the size of 6mm multiplied by 5mm multiplied by 4mm 9 O 15 Nonlinear optical crystal.
Example 30
Growth of LiSrB by hydrothermal method 9 O 15 Nonlinear optical crystal:
the compound LiSrB prepared according to example 1 9 O 15 Placing the polycrystalline powder into 20mL of deionized water for dissolution, and carrying out ultrasonic treatment on the incompletely dissolved mixture at the temperature of 60 ℃ to enable the incompletely dissolved mixture to be fully mixed and dissolved; by LiOH and Sr (OH) 2 Adjusting the pH value to 8;
transferring the obtained mixed solution into a clean and pollution-free lining of a high-pressure reaction kettle with the volume of 100mL, and screwing and sealing the reaction kettle;
placing the high-pressure reaction kettle in a constant temperature box, heating to 150 ℃, keeping the temperature for 8 days, and then cooling to room temperature at a cooling rate of 5 ℃/day; thus obtaining LiSrB with the size of 3mm multiplied by 2mm multiplied by 1mm 9 O 15 Nonlinear optical crystal.
Example 31
Growth of LiSrB by hydrothermal method 9 O 15 Nonlinear optical crystal：
The compound LiSrB prepared according to example 8 9 O 15 Placing the polycrystalline powder into 100mL of deionized water for dissolution, and carrying out ultrasonic treatment on the incompletely dissolved mixture at the temperature of 60 ℃ to enable the incompletely dissolved mixture to be fully mixed and dissolved; by LiOH and Sr (OH) 2 Adjusting the pH value to 11;
transferring the obtained mixed solution into a clean and pollution-free lining of a high-pressure reaction kettle with the volume of 100mL, and screwing and sealing the reaction kettle;
placing the high-pressure reaction kettle in a constant temperature box, heating to 350 ℃, keeping the temperature for 5 days, and then cooling to room temperature at a cooling rate of 20 ℃/day; thus obtaining LiSrB with the size of 5mm multiplied by 3mm 9 O 15 Nonlinear optical crystal.
Example 32
LiSrB growth by room temperature solution method 9 O 15 Nonlinear optical crystal:
the compound LiSrB prepared according to example 9 9 O 15 Placing the polycrystalline powder into a cleaned glass container, adding 20mL deionized water, and performing ultrasonic treatment to obtain a mixture, dissolving, and adding HF, liOH and Sr (OH) 2 Adjusting the pH value of the solution to 8, and filtering with filter paper to obtain a mixed solution;
placing the obtained mixed solution in a clean triangular bottle, sealing with weighing paper, placing in a static environment without shaking, pollution and air convection, punching a plurality of small holes on the sealing to regulate the evaporation rate of water in the aqueous solution, and standing for 5 days at room temperature;
when crystal particles grow out of the solution at the bottom of the container until the size of the crystal particles is not changed obviously, obtaining seed crystals;
selecting seed crystal with good quality, suspending in the obtained mixed solution, standing at room temperature for 30 days to obtain LiSrB with dimensions of 10mm×8mm×6mm 9 O 15 Nonlinear optical crystal.
Example 33
LiSrB growth by room temperature solution method 9 O 15 Nonlinear optical crystal:
prepared according to example 10Compound LiSrB of (2) 9 O 15 Placing the polycrystalline powder into a cleaned glass container, adding 100mL deionized water, and performing ultrasonic treatment to obtain a mixture, dissolving, and adding HF, liOH and Sr (OH) 2 Adjusting the pH value of the solution to 11, and filtering with filter paper to obtain a solution;
placing the obtained solution in a clean triangular bottle, sealing with weighing paper, placing in a static environment without shaking, pollution and air convection, punching a plurality of small holes on the sealing to regulate the evaporation rate of water in the aqueous solution, and standing for 20 days at room temperature;
when crystal particles grow out of the solution at the bottom of the container until the size of the crystal particles is not changed obviously, obtaining seed crystals;
selecting seed crystal with good quality, suspending in the obtained mixed solution, standing at room temperature for 30 days to obtain LiSrB with size of 5mm×4mm×3mm 9 O 15 Nonlinear optical crystal.
Example 34
Any LiSrB obtained in examples 15 to 33 9 O 15 The crystal is processed in the matching direction, and is arranged at the position 3 shown in figure 3, and at room temperature, a Q-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-Nd-YAG laser 1 to be injected into LiSrB 9 O 15 Single crystal 3, which produces green frequency doubling light with 532nm wavelength, and outputs about 0.5 times of the same condition KDP.
Claims (1)
1. A preparation method of a low-temperature Xiang Jiu lithium strontium borate nonlinear optical crystal is characterized in that the chemical formula of the crystal is LiSrB 9 O 15 Molecular weight is 431.85, which belongs to orthorhombic system, and space group isP2 1 2 1 2 1 The unit cell parameters area = 8.5432(5) Å，b = 8.6390(4) Å，c = 14.8622(8) Å，α = β= γ=90°, unit cell volume 1096.90 (10) a 3 The method comprises the steps of carrying out a first treatment on the surface of the Growing crystals by a melt method, a high Wen Rongye method, a vacuum packaging method, a hydrothermal method or a room temperature solution method;
the specific operation of growing the low-temperature Xiang Jiu lithium strontium borate nonlinear optical crystal by the melt method is carried out according to the following steps:
a. mixing Li-containing compound, sr-containing compound and B-containing compound uniformly according to a molar ratio of 1:1:9, loading into a platinum crucible, heating to 500-650 ℃ in a muffle furnace, and keeping the temperature for 24-120 hours to obtain the compound LiSrB 9 O 15 Polycrystalline powder of LiF and LiBO as Li-containing compound 2 、LiOH、Li 2 CO 3 、LiNO 3 、LiHCO 3 Or LiBF 4 The method comprises the steps of carrying out a first treatment on the surface of the The Sr-containing compound is SrF 2 、Sr(OH) 2 、SrCO 3 、Sr(NO 3 ) 2 、Sr(HCO 3 ) 2 Or Sr (BF 4 ) 2 The compound containing B is H 3 BO 3 Or B is a 2 O 3 ；
b. C, preparing a compound LiSrB obtained in the step a 9 O 15 Placing the polycrystalline powder into a platinum crucible, placing the crucible in a muffle furnace, heating to 650-850 ℃, and keeping the temperature for 10-120 hours to obtain a mixed melt;
c. slowly cooling the mixed melt obtained in the step b to 450 ℃ at the speed of 0.1-2 ℃/h, and rapidly cooling to room temperature at the speed of 5-10 ℃/h to obtain LiSrB 9 O 15 Seed crystal;
d. crystal growth in a compound melt using the Czochralski method: c, fixing the seed crystal obtained in the step c on a seed rod, applying 2-20rpm crystal rotation from the upper side of the mixed melt obtained in the step b through a crystal growth controller, lifting the seed crystal at the speed of 1-10 mm/day, simultaneously cooling to 600-840 ℃ at the speed of 0.1-10 ℃/h, and obtaining LiSrB after the crystal growth is stopped 9 O 15 A nonlinear optical crystal;
or growing crystals in a compound melt by a kyropoulos method: c, fixing the seed crystal obtained in the step c on a seed rod, dropping the seed crystal from the upper part of the melt prepared in the step b, cooling to 600-840 ℃ at the speed of 0.1-10 ℃/h, enabling the crystal to grow for 5-15 hours, slowly lifting the crystal but not separating from the liquid surface for continuous growth, repeating the steps, and obtaining LiSrB after the crystal growth is stopped 9 O 15 A nonlinear optical crystal;
or under a crucibleThe drop method grows crystals in the compound melt: placing the seed crystal prepared in the step c at the bottom of a crucible, and then placing the compound LiSrB prepared in the step a 9 O 15 Placing the polycrystal into a crucible, sealing the platinum crucible, placing the crucible in a growth furnace, raising the temperature of the growth furnace to 650-850 ℃, keeping the temperature constant for 10-120 hours, adjusting the position of the crucible to enable seed crystals to be micro-melted, lowering the crucible at the speed of 1-10 mm/day, simultaneously keeping the growth temperature unchanged or lowering the temperature at the highest speed of 3 ℃/h to 600-840 ℃, and after the growth is finished, quickly lowering the temperature to room temperature at the speed of 5-10 ℃/h to obtain LiSrB 9 O 15 A nonlinear optical crystal;
the specific operation of growing the low-temperature Xiang Jiu lithium strontium borate nonlinear optical crystal by the high-temperature melt method is carried out according to the following steps:
a. mixing Li-containing compound, sr-containing compound and B-containing compound uniformly according to a molar ratio of 1:1:9, loading into a platinum crucible, heating to 650-850 ℃ in a muffle furnace, and keeping the temperature for 24-120 hours to obtain the compound LiSrB 9 O 15 Polycrystalline powder of LiF and LiBO as Li-containing compound 2 、LiOH、Li 2 CO 3 、LiNO 3 、LiHCO 3 Or LiBF 4 The method comprises the steps of carrying out a first treatment on the surface of the The Sr-containing compound is SrF 2 、Sr(OH) 2 、SrCO 3 、Sr(NO 3 ) 2 、Sr(HCO 3 ) 2 Or Sr (BF 4 ) 2 The compound containing B is H 3 BO 3 Or B is a 2 O 3 ；
b. C, preparing a compound LiSrB obtained in the step a 9 O 15 Uniformly mixing polycrystalline powder and a fluxing agent according to a molar ratio of 1:0.1-6, then putting the mixture into a platinum crucible, heating to 650-850 ℃, and keeping the temperature for 5-120 hours to obtain a mixed solution, wherein the fluxing agent is H 3 BO 3 ，B 2 O 3 PbO or PbF 2 ；
c. Preparing seed crystals: c, placing the mixed solution obtained in the step b into a single crystal furnace, slowly reducing the temperature to 550 ℃ at the speed of 0.1-2 ℃/h, and rapidly reducing the temperature to room temperature at the speed of 5-10 ℃/h to obtain LiSrB 9 O 15 Seed crystal;
d. growing a crystal: the steps are as followsc, fixing the seed crystal obtained in step b on a seed rod, applying 2-20rpm crystal rotation through a crystal growth controller from the upper side of the mixed solution obtained in step b, cooling to 600-840 ℃ at a speed of 0.1-3 ℃/h, and obtaining LiSrB after crystal growth is stopped 9 O 15 A nonlinear optical crystal;
the specific operation of growing the low-temperature Xiang Jiu lithium strontium borate nonlinear optical crystal by the vacuum packaging method is carried out according to the following steps:
a. uniformly mixing a Li-containing compound, a Sr-containing compound and a B-containing compound according to a molar ratio of 1:1:9, placing the mixture in a muffle furnace, heating to 600-850 ℃, and keeping the temperature for 24-120 hours to obtain the compound LiSrB 9 O 15 Polycrystalline powder of LiF and LiBO as Li-containing compound 2 、LiOH、Li 2 CO 3 、LiNO 3 、LiHCO 3 Or LiBF 4 The method comprises the steps of carrying out a first treatment on the surface of the The Sr-containing compound is SrF 2 、Sr(OH) 2 、SrCO 3 、Sr(NO 3 ) 2 、Sr(HCO 3 ) 2 Or Sr (BF 4 ) 2 The compound containing B is H 3 BO 3 Or B is a 2 O 3 ；
b. C, preparing a compound LiSrB obtained in the step a 9 O 15 Uniformly mixing polycrystalline powder and fluxing agent according to a molar ratio of 1:0.1-6, filling into a quartz tube, sealing at high temperature, placing into a muffle furnace, heating to 550-800 ℃, keeping the temperature for 5-120 hours, cooling to 450 ℃ at a speed of 0.1-3 ℃/h, and rapidly cooling to room temperature at a speed of 5-10 ℃/h to obtain LiSrB 9 O 15 Nonlinear optical crystal, the fluxing agent is H 3 BO 3 ，B 2 O 3 PbO or PbF 2 ；
The specific operation of growing the low-temperature Xiang Jiu lithium strontium borate nonlinear optical crystal by the hydrothermal method is carried out according to the following steps:
a. mixing Li-containing compound, sr-containing compound and B-containing compound uniformly according to a molar ratio of 1:1:9, loading into a platinum crucible, heating to 500-650 ℃ in a muffle furnace, and keeping the temperature for 24-120 hours to obtain the compound LiSrB 9 O 15 Polycrystalline powder of LiF and LiBO as Li-containing compound 2 、LiOH、Li 2 CO 3 、LiNO 3 、LiHCO 3 Or LiBF 4 The method comprises the steps of carrying out a first treatment on the surface of the The Sr-containing compound is SrF 2 、Sr(OH) 2 、SrCO 3 、Sr(NO 3 ) 2 、Sr(HCO 3 ) 2 Or Sr (BF 4 ) 2 The compound containing B is H 3 BO 3 Or B is a 2 O 3 ；
b. C, preparing a compound LiSrB obtained in the step a 9 O 15 Dissolving the polycrystalline powder in 20-100-mL deionized water, ultrasonic treating at 60deg.C to obtain a mixture, mixing and dissolving with LiOH and Sr (OH) 2 Adjusting the pH value to 8-11;
c. transferring the mixed solution obtained in the step b into a clean and pollution-free lining of a high-pressure reaction kettle with the volume of 100mL, and screwing and sealing the reaction kettle;
d. placing the high-pressure reaction kettle in a constant temperature box, heating to 150-350 ℃, keeping the temperature for 5-8 days, and cooling to room temperature at a cooling rate of 5-20 ℃/day to obtain LiSrB 9 O 15 A nonlinear optical crystal;
the specific operation of growing the low-temperature Xiang Jiu lithium strontium borate nonlinear optical crystal by the room-temperature solution method is carried out according to the following steps:
a. mixing Li-containing compound, sr-containing compound and B-containing compound uniformly according to a molar ratio of 1:1:9, loading into a platinum crucible, heating to 450-760 ℃ in a muffle furnace, and keeping the temperature for 24-120 hours to obtain the compound LiSrB 9 O 15 The Li-containing compound is LiF, liBO 2 、LiOH、Li 2 CO 3 、LiNO 3 、LiHCO 3 Or LiBF 4 The method comprises the steps of carrying out a first treatment on the surface of the The Sr-containing compound is SrF 2 、Sr(OH) 2 、SrCO 3 、Sr(NO 3 ) 2 、Sr(HCO 3 ) 2 Or Sr (BF 4 ) 2 The compound containing B is H 3 BO 3 Or B is a 2 O 3 ；
b. C, preparing a compound LiSrB obtained in the step a 9 O 15 Placing the polycrystalline powder into a cleaned glass container, adding 20-100mL deionized water, performing ultrasonic treatment to thoroughly mix and dissolve, and using HFAnd LiOH and Sr (OH) 2 Adjusting pH to 8-11, and filtering with filter paper to obtain mixed solution;
c. placing the mixed solution obtained in the step b into a clean glass container, sealing with weighing paper, placing in a static environment without shaking, pollution and air convection, punching a plurality of small holes on the sealing to regulate the evaporation rate of water in the aqueous solution, and standing for 5-20 days at room temperature;
d. c, growing crystal particles on the bottom of the container until the crystal particle size is not changed obviously any more to obtain seed crystals;
e. selecting seed crystal with better quality in the step d, suspending the seed crystal in the mixed solution prepared in the step b, standing and growing for 10-30 days at room temperature to obtain LiSrB 9 O 15 Nonlinear optical crystal.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5684813A (en) * | 1995-10-26 | 1997-11-04 | The State Of Oregon Acting By And Through The Oregon State Board Of Higher Education On Behalf Of Oregon State University | Polyborates useful for optical frequency conversion |
| CN103436961A (en) * | 2013-08-07 | 2013-12-11 | 新疆紫晶光电技术有限公司 | Lithium strontium borate non-linear optical crystal as well as preparation method and application thereof |
| CN111334858A (en) * | 2020-03-06 | 2020-06-26 | 中国科学院新疆理化技术研究所 | Compound barium fluoborate, barium fluoborate nonlinear optical crystal, preparation method and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5684813A (en) * | 1995-10-26 | 1997-11-04 | The State Of Oregon Acting By And Through The Oregon State Board Of Higher Education On Behalf Of Oregon State University | Polyborates useful for optical frequency conversion |
| CN103436961A (en) * | 2013-08-07 | 2013-12-11 | 新疆紫晶光电技术有限公司 | Lithium strontium borate non-linear optical crystal as well as preparation method and application thereof |
| CN111334858A (en) * | 2020-03-06 | 2020-06-26 | 中国科学院新疆理化技术研究所 | Compound barium fluoborate, barium fluoborate nonlinear optical crystal, preparation method and application |
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| M=Ba and M′=Na)".International Journal of Inorganic Materials.2001,第3卷第1015-1023页. * |
| N. Penin et al.."Synthesis and crystal structure of three MM′B9O15 borates (M=Ba, Sr and M′=Li * |
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