CN114232093A - Compound zinc calcium borate, zinc calcium borate nonlinear optical crystal, preparation method and application - Google Patents
Compound zinc calcium borate, zinc calcium borate nonlinear optical crystal, preparation method and application Download PDFInfo
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- CN114232093A CN114232093A CN202111541879.7A CN202111541879A CN114232093A CN 114232093 A CN114232093 A CN 114232093A CN 202111541879 A CN202111541879 A CN 202111541879A CN 114232093 A CN114232093 A CN 114232093A
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- 239000013078 crystal Substances 0.000 title claims abstract description 342
- GUWHDOLCIHGFCW-UHFFFAOYSA-N [Ca+2].B([O-])([O-])[O-].[Zn+2] Chemical compound [Ca+2].B([O-])([O-])[O-].[Zn+2] GUWHDOLCIHGFCW-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 230000003287 optical effect Effects 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- -1 Compound zinc calcium borate Chemical class 0.000 title claims abstract description 20
- 229910004858 CaZn2 Inorganic materials 0.000 claims abstract description 86
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 128
- 238000001816 cooling Methods 0.000 claims description 94
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 54
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 36
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 28
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000011667 zinc carbonate Substances 0.000 claims description 17
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 17
- 239000012071 phase Substances 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 8
- 238000002441 X-ray diffraction Methods 0.000 claims description 6
- 230000004907 flux Effects 0.000 claims description 6
- ONIOAEVPMYCHKX-UHFFFAOYSA-N carbonic acid;zinc Chemical compound [Zn].OC(O)=O ONIOAEVPMYCHKX-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229940043430 calcium compound Drugs 0.000 claims description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 4
- FPHIOHCCQGUGKU-UHFFFAOYSA-L difluorolead Chemical compound F[Pb]F FPHIOHCCQGUGKU-UHFFFAOYSA-L 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000010431 corundum Substances 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims 2
- 229910004860 CaZn Inorganic materials 0.000 abstract description 35
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract 2
- 239000006184 cosolvent Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 34
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 31
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 28
- 239000007788 liquid Substances 0.000 description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 24
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 16
- 239000000920 calcium hydroxide Substances 0.000 description 16
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 16
- 239000011787 zinc oxide Substances 0.000 description 16
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 15
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 13
- 229940007718 zinc hydroxide Drugs 0.000 description 13
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 12
- 239000004327 boric acid Substances 0.000 description 12
- 229910052810 boron oxide Inorganic materials 0.000 description 12
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 12
- 229910052697 platinum Inorganic materials 0.000 description 12
- 235000004416 zinc carbonate Nutrition 0.000 description 12
- 229910002651 NO3 Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 7
- 125000005619 boric acid group Chemical group 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
-
- 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
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
-
- 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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- Crystallography & Structural Chemistry (AREA)
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
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Abstract
The invention relates to a compound calcium zinc borate, a calcium zinc borate nonlinear optical crystal, a preparation method and application thereof, wherein the chemical formula of the compound is CaZn2(BO3)2Molecular weight 288.44, synthesizing the compound by solid-phase reaction, the molecular formula of the crystal is CaZn2(BO3)2Molecular weight 288.44, orthorhombic, space groupAba2 unit cell parameters a =11.7579(7) a, b =8.5721(4) a, c =4.9421(3) a, Z =4, V =498.11(5) a3The cosolvent method is adopted to grow the crystal, and the powder frequency doubling effect of the crystal is about KDP (KH)2PO4) 3-4 times of that of the ultraviolet absorption material, wide light transmission wave band and ultraviolet absorption edge lower than 200 nm. By the method, the CaZn with the size of centimeter level is obtained2(BO3)2The nonlinear optical crystal is used for preparing harmonic light output or ultraviolet frequency doubling light output by 2 frequency doubling or 3 frequency doubling or 4 frequency doubling of 1064nm fundamental frequency light output by a Nd-YAG laser, or is used for preparing a frequency doubling generator, an upper frequency converter or a lower frequency converter or an optical parametric oscillator.
Description
Technical Field
The invention relates to a compound of calcium zinc borate CaZn2(BO3)2And a zinc calcium borate nonlinear optical crystal, a preparation method thereof and a nonlinear optical device manufactured by using the crystal.
Background
In order to obtain nonlinear optical material with nonlinear optical property, the current international common method is to introduce nonlinear optical functional elements which are easy to distort into the structure, and the elements mainly contain d0，d10Transition metal cation polyhedrons of electronic structure or metal cation polyhedrons containing lone electron pair. However, these structural elements often red-shift the uv cut edge of the material, making it unusable in the uv region. While borates are characterized by the advantage of transmitting UV radiation, many excellent nonlinear optical crystals have been found in borates, such as BBO (. beta. -BBO), LBO (LiB)3O5) Crystal, CBO (CsB)3O5) Crystal, CLBO (CsLiB)6O10) Crystal and KBBF (KBe)2BO3F2) And (4) crystals. Although the crystal growth techniques for these materials are becoming more sophisticated, there are still significant disadvantages: such as easy deliquescence of crystal, long growth period, serious lamellar growth habit, high price and the like. Therefore, the synthesis of new nonlinear optical crystal materials remains a very important and difficult task.
In the development of novel ultraviolet nonlinear optical crystals, people still select borate crystals with wide light transmission range and large laser damage threshold, and in order to further widen the light transmission range and enable the ultraviolet cut-off edge to reach deep ultraviolet, alkali metal or alkaline earth metal without d-d electronic transition is generally used as cations, and fluorine ions are introduced into the borate skeleton.
Disclosure of Invention
The invention aims to provide a compound calcium zinc borate, wherein the chemical formula of the compound is CaZn2(BO3)2Molecular weight 288.44, compound was synthesized by solid phase reaction.
Another object of the present invention is to provide a method for producingCompound calcium zinc borate nonlinear optical crystal with chemical formula of CaZn2(BO3)2Molecular weight 288.44, not having a center of symmetry, belonging to the orthorhombic system, space group Aba2(No.33), and unit cell parameters of
Z＝4，
The invention also aims to provide a compound synthesized by a solid-phase reaction method and a method for growing the zinc calcium borate nonlinear optical crystal by a high-temperature melt method.
The invention also aims to provide application of the zinc calcium borate nonlinear optical crystal.
The chemical formula of the compound of the invention is CaZn2(BO3)2Molecular weight 288.44, compound was synthesized by solid phase reaction.
A non-linear optical crystal of calcium zinc borate is disclosed, whose chemical formula is CaZn2(BO3)2Molecular weight 288.44, not having a center of symmetry, belonging to the orthorhombic system, space group Aba2(No.33), and unit cell parameters of
Z＝4，
The preparation method of the zinc calcium borate nonlinear optical crystal adopts a high-temperature melt method to grow the crystal, and the specific operation is carried out according to the following steps:
a. the calcium-containing compound is CaCO3、Ca(NO3)2Or Ca (OH)2(ii) a The zinc-containing compound is ZnO or ZnCO3、Zn(NO3)2Or Zn (OH)2(ii) a Containing boronThe compound is H3BO3Or B2O3Weighing and placing the materials into a mortar according to the molar ratio of 1:2:2, mixing and carefully grinding the materials, then placing the materials into an open corundum crucible with the diameter of 100mm multiplied by 100mm, placing the mixture into a muffle furnace, slowly heating the mixture to 600 ℃, keeping the temperature for 24 hours, cooling the mixture to room temperature, taking the mixture out, placing the mixture into the muffle furnace after the second grinding, heating the mixture to 650 ℃, keeping the temperature for 24 hours, cooling the mixture to room temperature, taking the mixture out, placing the mixture into the muffle furnace after the third grinding, heating the mixture to 850 ℃, keeping the temperature for 48 hours, taking the mixture out, grinding the mixture to obtain single-phase polycrystalline powder of a zinc borate calcium compound, performing X-ray analysis on the single-phase polycrystalline powder, and performing X-ray analysis on the obtained X-ray spectrogram and calcium zinc borate CaZn2(BO3)2The X-ray spectrograms obtained from the single crystal structures are consistent;
b. c, mixing the polycrystalline powder obtained in the step a and a fluxing agent CaF according to the molar ratio of 1:1-32、LiF、PbF2、LiF-H3BO3、LiF-NaF-H3BO3Or LiF-PbF2Uniformly mixing, heating to the temperature of 900-;
or directly using calcium-containing compound as CaCO3、Ca(NO3)2Or Ca (OH)2(ii) a The zinc-containing compound is ZnO or ZnCO3、Zn(NO3)2Or Zn (OH); the boron-containing compound is H3BO3Or B2O3With fluxing agent CaF2、LiF、PbF2、LiF-H3BO3、LiF-NaF-H3BO3Or LiF-PbF2Uniformly mixing the raw materials according to a molar ratio of 1:2:2:1-3, heating the mixture to 800 ℃ at a heating rate of 1-30 ℃/h, keeping the temperature for 5-80 hours, and cooling the mixture to 700 ℃ at 620 ℃ to obtain a mixed solution;
c. preparing zinc calcium borate seed crystals: b, slowly cooling the mixed solution obtained in the step b to room temperature at the speed of 0.5-10 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
d. c, fixing the seed crystal obtained in the step c on a seed crystal rod, lowering the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 5-60 minutes, lowering the seed crystal to the surface of the mixed melt or into the mixed melt for remelting, keeping the temperature for 5-60 minutes, and reducing the temperature to 620-700 ℃ at the speed of 1-60 ℃/h;
e. slowly cooling at the speed of 0.1-3 ℃/day, rotating the seed rod at the rotating speed of 1-60rpm to grow crystals, lifting the crystals away from the surface of the mixed melt after the single crystals grow to the required size, cooling to room temperature at the speed of 10-80 ℃/h, and taking out the crystals from a hearth to obtain the calcium zinc borate nonlinear optical crystals.
In step b, the fluxing agent LiF-H3BO3LiF and H in the system3BO3The molar ratio of (A) to (B) is 1: 1-3; LiF-PbF2LiF and PbF in the system2The molar ratio of (A) to (B) is 2-3: 1; LiF-NaF-H3BO3LiF, NaF and H in the system3BO3The molar ratio of (A) to (B) is 1-3:1-3: 1.
The zinc calcium borate nonlinear optical crystal is used for preparing a frequency doubling generator, an upper frequency converter, a lower frequency converter or an optical parametric oscillator.
The chemical formula of the zinc borate calcium compound is CaZn2(BO3)2The zinc borate calcium compound is prepared by adopting a solid phase reaction method according to the following chemical reaction formula:
CaCO3+2ZnO+2H3BO3→CaZn2(BO3)2+CO2↑+3H2O↑；
CaCO3+2ZnCO3+B2O3→CaZn2(BO3)2+3CO2↑；
CaCO3+2Zn(NO3)2+2H3BO3→CaZn2(BO3)2+CO2↑+3H2O↑+4NO2↑；
CaCO3+2Zn(OH)2+B2O3→CaZn2(BO3)2+CO2↑+2H2O↑
Ca(NO3)2+2ZnO+2H3BO3→CaZn2(BO3)2+2NO2↑+3H2O↑
Ca(NO3)2+2ZnCO3+B2O3→CaZn2(BO3)2+2NO2↑+2CO2↑
Ca(NO3)2+2Zn(NO3)2+2H3BO3→CaZn2(BO3)2+6NO2↑+3H2O↑
Ca(NO3)2+2Zn(OH)2+B2O3→CaZn2(BO3)2+2NO2↑+2H2O↑
Ca(OH)2+2ZnO+2H3BO3→CaZn2(BO3)2+4H2O↑
Ca(OH)2+2ZnCO3+B2O3→CaZn2(BO3)2+2H2O↑+2CO2↑
Ca(OH)2+2Zn(NO3)2+2H3BO3→CaZn2(BO3)2+4NO2↑+4H2O↑
Ca(OH)2+2Zn(OH)2+B2O3→CaZn2(BO3)2+2NO2↑+3H2O↑
the obtained crystal has the advantages of wider light-transmitting wave band, higher hardness, good mechanical property, difficult cracking and deliquescence, easy processing and storage and the like. The nonlinear optical device prepared by the compound zinc calcium borate nonlinear optical crystal obtained by the method uses Nd-YAG Q-switched laser as a light source at room temperature, enters infrared light with the wavelength of 1064nm, outputs green laser with the wavelength of 532nm, and has the laser intensity equivalent to KDP (KH)2PO4) 3-4 times of the total weight of the product.
Drawings
FIG. 1 is an X-ray diffraction pattern of an experimental powder of the present invention;
FIG. 2 shows CaZn of the present invention2(BO3)2A crystal structure;
FIG. 3 is a schematic diagram of the operation of the nonlinear optical device of the present invention, which includes (1) a laser, (2) a full focusing lens, and (3) CaZn2(BO3)2The nonlinear optical crystal, (4) is a beam splitter prism, and (5) is a filter plate.
Detailed Description
The invention is described in detail below with reference to the following figures and examples:
example 1
According to the reaction formula: CaCO3+2ZnO+2H3BO3→CaZn2(BO3)2+CO2↑+3H2O ↓ [ O ] preparation CaZn2(BO3)2Nonlinear optical crystal:
a. CaCO is added according to a molar ratio of 1:2:23ZnO and H3BO3Placing into mortar, mixing, grinding, placing into opening corundum crucible of phi 100mm × 100mm, placing into muffle furnace, slowly heating to 600 deg.C, holding temperature for 24 hr, cooling to room temperature, taking out, grinding for the second time, placing into muffle furnace, heating to 650 deg.C, holding temperature for 24 hr, cooling to room temperature, grinding for the third time, placing into muffle furnace, heating to 850 deg.C, holding temperature for 48 hr, taking out, grinding to obtain single-phase polycrystalline powder of zinc calcium borate, and performing X-ray analysis to the obtained product, wherein the obtained X-ray spectrogram and calcium zinc borate CaZn2(BO3)2The X-ray spectrograms obtained from the single crystal structures are consistent;
b. b, mixing the calcium zinc borate CaZn obtained in the step a2(BO3)2Compound polycrystalline powder and fluxing agent LiF are mixed according to the mol ratio of 1:1, the mixture is put into an open platinum crucible with the diameter of phi 100mm multiplied by 100mm, the mixture is heated to 1000 ℃ at the heating rate of 30 ℃/h, the temperature is kept for 80 hours, and then the temperature is reduced to 800 ℃ to obtain mixed solution;
c. preparation of CaZn2(BO3)2Seed crystal: c, slowly cooling the mixed solution obtained in the step b to room temperature at the speed of 10 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
d. in thatGrowing crystals in the compound melt: c, adding CaZn obtained in the step c2(BO3)2Seed crystals are fixed on a seed crystal rod and are discharged from the top of a crystal growing furnace, the seed crystals are preheated on the surface of the mixed melt for 60 minutes and immersed in the liquid level, the seed crystals are melted back in the mixed melt, the temperature is kept for 60 minutes, and the temperature is reduced to 700 ℃ at the speed of 60 ℃/h;
e. cooling at a rate of 3 ℃/day, rotating the seed rod at a rotating speed of 60rpm, separating the crystal from the liquid surface after the crystal growth is finished, and cooling to room temperature at a rate of 80 ℃/hour to obtain CaZn with the size of 26mm multiplied by 20mm multiplied by 10mm2(BO3)2A nonlinear optical crystal.
The raw material calcium carbonate in the reaction formula can be replaced by calcium nitrate, calcium hydroxide and calcium oxalate; the zinc oxide can be replaced by zinc carbonate, zinc hydroxide and zinc nitrate; boric acid may be replaced by boron oxide.
Example 2
According to the reaction formula: CaCO3+2ZnCO3+B2O3→CaZn2(BO3)2+3CO2↓ [ O ] synthetic CaZn2(BO3)2Preparation of CaZn2(BO3)2Nonlinear optical crystal:
preparation of single-phase polycrystalline powder of calcium zinc borate compound was carried out according to example 1:
the synthesized calcium zinc borate CaZn2(BO3)2Compound polycrystalline powder and fluxing agent LiF are mixed according to the mol ratio of 1:3, the mixture is put into an open platinum crucible with the diameter of phi 100mm multiplied by 100mm, the mixture is heated to 950 ℃ at the heating rate of 15 ℃/h, the temperature is kept for 70 hours, and then the mixture is cooled to 780 ℃ to obtain mixed solution;
preparation of CaZn2(BO3)2Seed crystal: slowly cooling the obtained mixed solution to room temperature at the speed of 8 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
growing crystals in a compound melt: the CaZn obtained2(BO3)2The seed crystal is fixed on the seed crystal rod and is arranged below the top of the crystal growing furnace, and is preheated on the surface of the mixed meltSoaking the seed crystal in the liquid surface for 50 minutes to melt the seed crystal back in the mixed melt, keeping the temperature for 50 minutes, and reducing the temperature to 680 ℃ at the speed of 45 ℃/h;
cooling at a speed of 2 ℃/day, rotating the seed rod at a speed of 50rpm, separating the crystal from the liquid surface after the crystal growth is finished, and cooling to room temperature at a speed of 70 ℃/hour to obtain CaZn with the size of 25mm multiplied by 22mm multiplied by 13mm2(BO3)2And (4) crystals.
The raw material calcium carbonate in the reaction formula can be replaced by calcium nitrate, calcium hydroxide and calcium oxalate; the zinc carbonate can be replaced by zinc oxide, zinc hydroxide and zinc nitrate; the boron oxide may be replaced with boric acid.
Example 3
According to the reaction formula: CaCO3+2Zn(NO3)2+2H3BO3→CaZn2(BO3)2+CO2↑+3H2O↑+4NO2Preparation of CaZn from ↓2(BO3)2Nonlinear optical crystal:
preparation of single-phase polycrystalline powder of calcium zinc borate compound was carried out according to example 1:
the synthesized calcium zinc borate CaZn2(BO3)2Compound polycrystalline powder and flux PbF2Mixing according to the mol ratio of 1:2, putting into an opening platinum crucible with the diameter of 100mm multiplied by 100mm, heating to 900 ℃ at the heating rate of 15 ℃/h, keeping the temperature for 5 hours, and then cooling to 650 ℃ to obtain a mixed melt;
preparation of CaZn2(BO3)2Seed crystal: slowly cooling the obtained mixed solution to room temperature at the speed of 1 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
growing crystals in a compound melt: the CaZn obtained2(BO3)2Seed crystals are fixed on a seed crystal rod and are discharged from the top of a crystal growing furnace, the seed crystals are preheated on the surface of the mixed melt for 5 minutes and immersed in the liquid level, the seed crystals are melted back in the mixed melt, the temperature is kept for 5 minutes, and the temperature is reduced to 620 ℃ at the speed of 1 ℃/h;
then at a rate of 0.1 deg.C/dayCooling, rotating the seed rod at a rotation speed of 1rpm, separating the crystal from the liquid surface after the crystal growth is finished, and cooling to room temperature at a speed of 10 ℃/hour to obtain CaZn with the size of 30mm multiplied by 17mm multiplied by 10mm2(BO3)2And (4) crystals.
The raw material calcium carbonate in the reaction formula can be replaced by calcium nitrate, calcium hydroxide and calcium oxalate; the zinc nitrate can be replaced by zinc oxide, zinc hydroxide and zinc carbonate; boric acid may be replaced by boron oxide.
Example 4
According to the reaction formula: CaCO3+2Zn(OH)2+B2O3→CaZn2(BO3)2+CO2↑+2H2O ↓ [ O ] preparation CaZn2(BO3)2Nonlinear optical crystal:
preparation of single-phase polycrystalline powder of calcium zinc borate compound was carried out according to example 1:
the synthesized calcium zinc borate CaZn2(BO3)2Compound polycrystalline powder and flux PbF2Mixing according to the molar ratio of 1:1, placing into a platinum crucible with an opening of phi 100mm multiplied by 100mm, heating to 900 ℃ at the heating rate of 15 ℃/h, keeping the temperature for 5 hours, and cooling to 650 ℃ to obtain a mixed melt;
preparation of CaZn2(BO3)2Seed crystal: slowly cooling the obtained mixed solution to room temperature at the speed of 5 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
growing crystals in a compound melt: the CaZn obtained2(BO3)2Seed crystals are fixed on a seed crystal rod and are discharged from the top of a crystal growing furnace, the seed crystals are preheated on the surface of the mixed melt for 5 minutes and immersed in the liquid level, the seed crystals are melted back in the mixed melt, the temperature is kept for 5 minutes, and the temperature is reduced to 620 ℃ at the speed of 1 ℃/h;
cooling at a rate of 0.1 deg.C/day, rotating seed rod at 1rpm, separating the crystal from the liquid surface after the crystal growth is finished, and cooling to room temperature at a rate of 10 deg.C/hr to obtain CaZn with dimensions of 31mm × 19mm × 10mm2(BO3)2And (4) crystals.
The raw material calcium carbonate in the reaction formula can be replaced by calcium nitrate, calcium hydroxide and calcium oxalate; the zinc hydroxide can be replaced by zinc oxide, zinc nitrate and zinc carbonate; the boron oxide may be replaced by boric acid.
Example 5
According to the reaction formula: ca (NO)3)2+2ZnO+2H3BO3→CaZn2(BO3)2+2NO2↑+3H2O ↓ [ O ] preparation CaZn2(BO3)2Nonlinear optical crystal:
preparation of single-phase polycrystalline powder of calcium zinc borate compound was carried out according to example 1:
the synthesized calcium zinc borate CaZn2(BO3)2Compound polycrystalline powder and flux LiF-H3BO3Mixing according to the mol ratio of 1:1:1, placing into an opening platinum crucible with the diameter of 100mm multiplied by 100mm, heating to 900 ℃ at the heating rate of 1 ℃/h, keeping the temperature for 25 hours, and then cooling to 760 ℃ to obtain a mixed melt;
preparation of CaZn2(BO3)2Seed crystal: slowly cooling the obtained mixed solution to room temperature at the speed of 0.5 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
growing crystals in a compound melt: the CaZn obtained2(BO3)2Fixing seed crystals on a seed crystal rod, descending the seed crystals from the top of a crystal growth furnace, preheating the seed crystals on the surface of the mixed melt for 25 minutes, immersing the seed crystals in the liquid level, melting the seed crystals in the mixed melt back, keeping the temperature for 25 minutes, and reducing the temperature to 630 ℃ at a speed of 15 ℃/h;
cooling at a rate of 0.8 ℃/day, rotating the seed rod at a rotating speed of 15rpm, separating the crystal from the liquid surface after the crystal growth is finished, and cooling to room temperature at a rate of 80 ℃/hour to obtain CaZn with the size of 30mm multiplied by 22mm multiplied by 13mm2(BO3)2And (4) crystals.
The raw material calcium nitrate in the reaction formula can be replaced by calcium carbonate, calcium hydroxide and calcium oxalate; the zinc oxide can be replaced by zinc nitrate, zinc hydroxide and zinc carbonate; boric acid may be replaced by boron oxide.
Example 6
Preparation of single-phase polycrystalline powder of calcium zinc borate compound was carried out according to example 1:
according to the reaction formula: ca (NO)3)2+2ZnCO3+B2O3→CaZn2(BO3)2+2NO2↑+2CO2Preparation of CaZn from ↓2(BO3)2Nonlinear optical crystal:
the synthesized calcium zinc borate CaZn2(BO3)2Compound polycrystalline powder and flux LiF-H3BO3Mixing according to the mol ratio of 1:1:2, putting into an opening platinum crucible with the diameter of 100mm multiplied by 100mm, heating to 920 ℃ at the heating rate of 1 ℃/h, keeping the temperature for 30 hours, and then cooling to 740 ℃ to obtain mixed melt;
preparation of CaZn2(BO3)2Seed crystal: slowly cooling the obtained mixed solution to room temperature at the speed of 2 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
growing crystals in a compound melt: the CaZn obtained2(BO3)2Seed crystals are fixed on a seed crystal rod and are discharged from the top of a crystal growing furnace, the seed crystals are preheated on the surface of the mixed melt for 15 minutes and immersed in the liquid level, the seed crystals are melted back in the mixed melt, the temperature is kept for 15 minutes, and the temperature is reduced to 625 ℃ at a speed of 60 ℃/h;
cooling at a rate of 3 ℃/day, rotating the seed rod at a rotating speed of 5rpm, separating the crystal from the liquid surface after the crystal growth is finished, and cooling to room temperature at a rate of 50 ℃/hour to obtain CaZn with the size of 33mm multiplied by 19mm multiplied by 13mm2(BO3)2And (4) crystals.
The raw material calcium nitrate in the reaction formula can be replaced by calcium carbonate, calcium hydroxide and calcium oxalate; the zinc carbonate can be replaced by zinc oxide, zinc hydroxide and zinc nitrate; the boron oxide may be replaced with boric acid.
Example 7
According to the reaction formula: ca (NO)3)2+2Zn(NO3)2+2H3BO3→CaZn2(BO3)2+6NO2↑+3H2O ↓ [ O ] preparation CaZn2(BO3)2Nonlinear optical crystal:
preparation of single-phase polycrystalline powder of calcium zinc borate compound was carried out according to example 1:
the synthesized calcium zinc borate CaZn2(BO3)2Compound polycrystalline powder and fluxing agent LiF-PbF2Mixing according to the mol ratio of 1:2:1, placing into an opening platinum crucible with the diameter of 100mm multiplied by 100mm, heating to 940 ℃ at the heating rate of 1 ℃/h, keeping the temperature for 40 hours, and then cooling to 800 ℃ to obtain a mixed melt;
preparation of CaZn2(BO3)2Seed crystal: slowly cooling the obtained mixed solution to room temperature at the speed of 15 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
growing crystals in a compound melt: the CaZn obtained2(BO3)2Fixing seed crystals on a seed crystal rod, descending the seed crystals from the top of a crystal growth furnace, preheating the seed crystals on the surface of the mixed melt for 35 minutes, immersing the seed crystals in the liquid level, melting the seed crystals in the mixed melt back, keeping the temperature for 35 minutes, and reducing the temperature to 680 ℃ at a speed of 25 ℃/h;
cooling at a rate of 3 ℃/day, rotating the seed rod at a rotating speed of 15rpm, separating the crystal from the liquid surface after the crystal growth is finished, and cooling to room temperature at a rate of 40 ℃/hour to obtain CaZn with the size of 19mm multiplied by 18mm multiplied by 11mm2(BO3)2And (4) crystals.
The raw material calcium nitrate in the reaction formula can be replaced by calcium carbonate, calcium hydroxide and calcium oxalate; the zinc carbonate can be replaced by zinc oxide, zinc hydroxide and zinc nitrate; boric acid may be replaced by boron oxide.
Example 8
According to the reaction formula: ca (NO)3)2+2Zn(OH)2+B2O3→CaZn2(BO3)2+2NO2↑+2H2O ↓ [ O ] preparation CaZn2(BO3)2Nonlinear optical crystal:
preparation of single-phase polycrystalline powder of calcium zinc borate compound was carried out according to example 1:
the synthesized calcium zinc borate CaZn2(BO3)2Compound polycrystalline powder and fluxing agent LiF-PbF2Mixing according to the mol ratio of 1:3:1, putting into an opening platinum crucible with the diameter of 100mm multiplied by 100mm, heating to 980 ℃ at the heating rate of 1 ℃/h, keeping the temperature for 40 hours, and cooling to 780 ℃ to obtain a mixed melt;
preparation of CaZn2(BO3)2Seed crystal: slowly cooling the obtained mixed solution to room temperature at the speed of 25 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
growing crystals in a compound melt: the CaZn obtained2(BO3)2Fixing seed crystals on a seed crystal rod, preheating the seed crystals on the surface of the mixed melt for 40 minutes from the top of a crystal growing furnace, immersing the seed crystals in the liquid level, melting the seed crystals in the mixed melt, keeping the temperature for 45 minutes, and reducing the temperature to 660 ℃ at a speed of 10 ℃/h;
cooling at a rate of 4 ℃/day, rotating the seed rod at a rotating speed of 25rpm, separating the crystal from the liquid surface after the crystal growth is finished, and cooling to room temperature at a rate of 30 ℃/hour to obtain CaZn with the size of 29mm multiplied by 17mm multiplied by 10mm2(BO3)2And (4) crystals.
The raw material calcium nitrate in the reaction formula can be replaced by calcium carbonate, calcium hydroxide and calcium oxalate; the zinc hydroxide can be replaced by zinc carbonate, zinc hydroxide and zinc nitrate; the boron oxide may be replaced with boric acid.
Example 9
According to the reaction formula: ca (OH)2+2ZnO+2H3BO3→CaZn2(BO3)2+4H2O ↓ [ O ] preparation CaZn2(BO3)2Nonlinear optical crystal:
preparation of single-phase polycrystalline powder of calcium zinc borate compound was carried out according to example 1:
the synthesized calcium zinc borate CaZn2(BO3)2Compound polycrystalline powder and fluxing agent LiF-NaF-H3BO3Mixing according to the molar ratio of 1:1:1:1Mixing, placing into a platinum crucible with an opening of phi 100mm multiplied by 100mm, heating to 900 ℃ at a heating rate of 15 ℃/h, keeping the temperature for 45 hours, and then cooling to 780 ℃ to obtain a mixed melt;
preparation of CaZn2(BO3)2Seed crystal: slowly cooling the obtained mixed solution to room temperature at the speed of 20 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
growing crystals in a compound melt: the CaZn obtained2(BO3)2Seed crystals are fixed on a seed crystal rod and are discharged from the top of a crystal growing furnace, the seed crystals are preheated on the surface of the mixed melt for 45 minutes and immersed in the liquid level, the seed crystals are melted back in the mixed melt, the temperature is kept for 40 minutes, and the temperature is reduced to 620 ℃ at the speed of 15 ℃/h;
cooling at a rate of 4 ℃/day, rotating the seed rod at a rotating speed of 28rpm, separating the crystal from the liquid surface after the crystal growth is finished, and cooling to room temperature at a rate of 38 ℃/hour to obtain CaZn with the size of 19mm multiplied by 27mm multiplied by 10mm2(BO3)2And (4) crystals.
The raw material calcium hydroxide in the reaction formula can be replaced by calcium carbonate, calcium nitrate and calcium oxalate; the zinc oxide can be replaced by zinc carbonate, zinc hydroxide and zinc nitrate; boric acid may be replaced by boron oxide.
Example 10
According to the reaction formula: ca (OH)2+2ZnCO3+B2O3→CaZn2(BO3)2+2H2O↑+2CO2Preparation of CaZn from ↓2(BO3)2Nonlinear optical crystal:
preparation of single-phase polycrystalline powder of calcium zinc borate compound was carried out according to example 1:
the synthesized calcium zinc borate CaZn2(BO3)2Compound polycrystalline powder and fluxing agent LiF-NaF-H3BO3Mixing according to the mol ratio of 1:3:1:3, putting into an opening platinum crucible with the diameter of 100mm multiplied by 100mm, heating to 920 ℃ at the heating rate of 25 ℃/h, keeping the temperature for 45 hours, and then cooling to 760 ℃ to obtain mixed melt;
preparation ofCaZn2(BO3)2Seed crystal: slowly cooling the obtained mixed solution to room temperature at the speed of 25 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
growing crystals in a compound melt: the CaZn obtained2(BO3)2Seed crystals are fixed on a seed crystal rod and are discharged from the top of a crystal growing furnace, the seed crystals are preheated on the surface of the mixed melt for 5 minutes and immersed in the liquid level, so that the seed crystals are melted back in the mixed melt, the temperature is kept for 5 minutes, and the temperature is reduced to 630 ℃ at the speed of 45 ℃/h;
cooling at a rate of 5 ℃/day, rotating the seed rod at a rotating speed of 25rpm, separating the crystal from the liquid surface after the crystal growth is finished, and cooling to room temperature at a rate of 40 ℃/hour to obtain CaZn with the size of 23mm multiplied by 17mm multiplied by 10mm2(BO3)2And (4) crystals.
The raw material calcium hydroxide in the reaction formula can be replaced by calcium carbonate, calcium nitrate and calcium oxalate; the zinc carbonate can be replaced by zinc hydroxide, zinc oxide and zinc nitrate; the boron oxide may be replaced with boric acid.
Example 11
According to the reaction formula: ca (OH)2+2Zn(NO3)2+2H3BO3→CaZn2(BO3)2+4NO2↑+4H2O ↓ [ O ] preparation CaZn2(BO3)2Nonlinear optical crystal:
preparation of single-phase polycrystalline powder of calcium zinc borate compound was carried out according to example 1:
the synthesized calcium zinc borate CaZn2(BO3)2Compound polycrystalline powder and fluxing agent LiF-PbF2Mixing according to the mol ratio of 1:1:1, putting into an opening platinum crucible with the diameter of 100mm multiplied by 100mm, heating to 900 ℃ at the heating rate of 25 ℃/h, keeping the temperature for 45 hours, and cooling to 740 ℃ to obtain mixed melt;
preparation of CaZn2(BO3)2Seed crystal: slowly cooling the obtained mixed solution to room temperature at the speed of 25 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
in the compoundGrowing crystals in the melt: the CaZn obtained2(BO3)2Seed crystals are fixed on a seed crystal rod and are discharged from the top of a crystal growing furnace, the seed crystals are preheated on the surface of the mixed melt for 25 minutes and immersed in the liquid level, the seed crystals are melted back in the mixed melt, the temperature is kept for 25 minutes, and the temperature is reduced to 640 ℃ at the speed of 45 ℃/h;
cooling at a rate of 5 ℃/day, rotating the seed rod at a rotating speed of 25rpm, separating the crystal from the liquid surface after the crystal growth is finished, and cooling to room temperature at a rate of 40 ℃/hour to obtain CaZn with the size of 20mm multiplied by 17mm multiplied by 9mm2(BO3)2And (4) crystals.
The raw material calcium hydroxide in the reaction formula can be replaced by calcium carbonate, calcium nitrate and calcium oxalate; the zinc nitrate can be replaced by zinc hydroxide, zinc oxide and zinc carbonate; boric acid may be replaced by boron oxide.
Example 12
According to the reaction formula: ca (OH)2+2Zn(OH)2+B2O3→CaZn2(BO3)2+2NO2↑+3H2O ↓ [ O ] synthetic CaZn2(BO3)2Preparation of CaZn2(BO3)2Nonlinear optical crystal:
preparation of single-phase polycrystalline powder of calcium zinc borate compound was carried out according to example 1:
the synthesized calcium zinc borate CaZn2(BO3)2Compound polycrystalline powder and fluxing agent LiF-PbF2Mixing according to the mol ratio of 1:1:3, placing into an opening platinum crucible with the diameter of 100mm multiplied by 100mm, heating to 1000 ℃ at the heating rate of 25 ℃/h, keeping the temperature for 25 hours, and then cooling to 790 ℃ to obtain a mixed melt;
preparation of CaZn2(BO3)2Seed crystal: slowly cooling the obtained mixed solution to room temperature at the speed of 15 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
growing crystals in a compound melt: the CaZn obtained2(BO3)2The seed crystal is fixed on the seed crystal rod and is arranged below the top of the crystal growing furnace, firstly on the surface of the mixed meltPreheating seed crystals for 25 minutes, immersing the seed crystals in the liquid level, melting the seed crystals back in the mixed melt, keeping the temperature for 25 minutes, and reducing the temperature to 700 ℃ at a speed of 45 ℃/h;
cooling at a rate of 3.5 ℃/day, rotating the seed rod at a rotating speed of 60rpm, separating the crystal from the liquid surface after the crystal growth is finished, and cooling to room temperature at a rate of 40 ℃/hour to obtain CaZn with the size of 24mm multiplied by 18mm multiplied by 13mm2(BO3)2And (4) crystals.
The raw material calcium hydroxide in the reaction formula can be replaced by calcium carbonate, calcium nitrate and calcium oxalate; the zinc hydroxide can be replaced by zinc nitrate, zinc oxide and zinc carbonate; the boron oxide may be replaced with boric acid.
Example 13
According to the reaction formula: CaCO3+2Zn(NO3)2+2H3BO3→CaZn2(BO3)2+CO2↑+3H2O↑+4NO2Preparation of CaZn from ↓2(BO3)2Nonlinear optical crystal:
CaCO is directly added according to the molar ratio of 1:2:2:13，Zn(NO3)2，H3BO3Uniformly mixing the flux and LiF, heating to 650 ℃ at the heating rate of 1 ℃/h, keeping the temperature for 5 hours, and cooling to 630 ℃ to obtain a mixed solution;
preparing zinc calcium borate seed crystals: c, slowly cooling the mixed solution obtained in the step b to room temperature at the speed of 0.5 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
fixing the obtained seed crystal on a seed crystal rod, feeding the seed crystal from the top of a crystal growth furnace, preheating the seed crystal for 5 minutes, feeding the seed crystal to the surface contacting with the mixed melt for remelting, keeping the temperature for 5 minutes, and reducing the temperature to 620 ℃ at the rate of 1 ℃/h;
slowly cooling at the speed of 0.1 ℃/day, rotating the seed rod at the rotating speed of 1rpm to grow crystals, lifting the crystals away from the surface of the mixed melt after the single crystals grow to the required size, cooling to room temperature at the speed of 10 ℃/h, and taking out the crystals from the hearth to obtain the calcium zinc borate nonlinear optical crystals with the size of 19mm multiplied by 16mm multiplied by 11 mm.
Example 14
According to the reaction formula: ca (OH)2+2ZnO+2H3BO3→CaZn2(BO3)2+4H2O ↓ [ O ] preparation CaZn2(BO3)2Nonlinear optical crystal:
directly adding Ca (OH) according to the molar ratio of 1:2:2:22，ZnO，H3BO3And the fluxing agent is PbF2Uniformly mixing, heating to 700 ℃ at a heating rate of 10 ℃/h, keeping the temperature for 50 hours, and then cooling to 650 ℃ to obtain a mixed melt;
preparing zinc calcium borate seed crystals: c, slowly cooling the mixed solution obtained in the step b to room temperature at the speed of 5 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
fixing the obtained seed crystal on a seed crystal rod, feeding the seed crystal from the top of a crystal growth furnace, preheating the seed crystal for 20 minutes, feeding the seed crystal into the mixed melt for remelting, keeping the temperature for 20 minutes, and reducing the temperature to 630 ℃ at a speed of 10 ℃/h;
and slowly cooling at the speed of 1 ℃/day, rotating the seed rod at the rotating speed of 10rpm to grow crystals, lifting the crystals away from the surface of the mixed melt after the single crystals grow to the required size, cooling to room temperature at the speed of 30 ℃/h, and taking out the crystals from a hearth to obtain the calcium zinc borate nonlinear optical crystals with the size of 22mm multiplied by 16mm multiplied by 9 mm.
Example 15
According to the reaction formula: ca (OH)2+2Zn(OH)2+B2O3→CaZn2(BO3)2+2NO2↑+3H2O ↓ [ O ] preparation CaZn2(BO3)2Nonlinear optical crystal:
directly adding Ca (OH) according to the molar ratio of 1:2:2:32，Zn(OH)2，B2O3And the fluxing agent is LiF-H3BO3Mixing uniformly, wherein LiF-H3BO3LiF and H in the system3BO3The molar ratio of (1: 1), heating to 800 ℃ at the heating rate of 15 ℃/h, keeping the temperature for 50 hours, cooling to 700 ℃,obtaining a mixed molten liquid;
preparing zinc calcium borate seed crystals: slowly cooling the obtained mixed solution to room temperature at the speed of 5 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
fixing the obtained seed crystal on a seed crystal rod, feeding the seed crystal from the top of a crystal growth furnace, preheating the seed crystal for 15 minutes, feeding the seed crystal to the surface contacting with the mixed melt for remelting, keeping the temperature for 25 minutes, and reducing the temperature to 680 ℃ at the rate of 20 ℃/h;
slowly cooling at the speed of 0.5 ℃/day, rotating the seed rod at the rotating speed of 60rpm to grow crystals, lifting the crystals away from the surface of the mixed melt after the single crystals grow to the required size, cooling to room temperature at the speed of 80 ℃/h, and taking out the crystals from the hearth to obtain the calcium zinc borate nonlinear optical crystals with the size of 25mm multiplied by 20mm multiplied by 10 mm.
Example 16
According to the reaction formula: ca (NO)3)2+2ZnCO3+B2O3→CaZn2(BO3)2+2NO2↑+2CO2Preparation of CaZn from ↓2(BO3)2Nonlinear optical crystal:
directly adding Ca (NO) according to the molar ratio of 1:2:1:23)2，Zn(NO3)2，B2O3The fluxing agent is LiF-NaF-H3BO3Mixing uniformly, wherein LiF-NaF-H3BO3LiF, NaF and H in the system3BO3The molar ratio of (1: 1: 1), heating to 780 ℃ at the heating rate of 25 ℃/h, keeping the temperature for 45 hours, and then cooling to 700 ℃ to obtain a mixed melt;
preparing zinc calcium borate seed crystals: slowly cooling the obtained mixed solution to room temperature at the speed of 10 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
fixing the obtained seed crystal on a seed crystal rod, feeding the seed crystal from the top of a crystal growth furnace, preheating the seed crystal for 60 minutes, feeding the seed crystal into the mixed melt for remelting, keeping the temperature for 60 minutes, and reducing the temperature to 640 ℃ at the speed of 60 ℃/h;
slowly cooling at the speed of 3 ℃/day, rotating the seed rod at the rotating speed of 60rpm to grow crystals, lifting the crystals away from the surface of the mixed melt after the single crystals grow to the required size, cooling to room temperature at the speed of 80 ℃/h, and taking out the crystals from a hearth to obtain the calcium zinc borate nonlinear optical crystals with the size of 23mm multiplied by 16mm multiplied by 9 mm.
Example 17
According to the reaction formula: CaCO3+2ZnO+2H3BO3→CaZn2(BO3)2+CO2↑+3H2O ↓ [ O ] preparation CaZn2(BO3)2Nonlinear optical crystal:
CaCO is directly added according to the molar ratio of 1:2:2:13，ZnO，H3BO3The fluxing agent is LiF-PbF2Mixing uniformly, wherein LiF-PbF2LiF and PbF in the system2The molar ratio of the mixture to the molten metal is 2:1, the mixture is heated to 800 ℃ at the heating rate of 20 ℃/h, the temperature is kept for 60 hours, and then the mixture is cooled to 690 ℃ to obtain a mixed molten liquid;
preparing zinc calcium borate seed crystals: slowly cooling the obtained mixed solution to room temperature at the speed of 8 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
fixing the obtained seed crystal on a seed crystal rod, feeding the seed crystal from the top of a crystal growth furnace, preheating the seed crystal for 50 minutes, feeding the seed crystal into the mixed melt for remelting, keeping the temperature for 50 minutes, and reducing the temperature to 630 ℃ at the rate of 30 ℃/h;
slowly cooling at the speed of 1.5 ℃/day, rotating the seed rod at the rotating speed of 40rpm to grow crystals, lifting the crystals away from the surface of the mixed melt after the single crystals grow to the required size, cooling to room temperature at the speed of 60 ℃/h, and taking out the crystals from a hearth to obtain the calcium zinc borate nonlinear optical crystals with the size of 25mm multiplied by 15mm multiplied by 10 mm.
Example 18
According to the reaction formula: ca (OH)2+2Zn(OH)2+B2O3→CaZn2(BO3)2+2NO2↑+3H2O ↓ [ O ] preparation CaZn2(BO3)2Nonlinear optical crystal:
in mole ratioThe ratio of 1:2:1:2 directly adds Ca (OH)2，Zn(OH)2，B2O3And the fluxing agent is LiF-H3BO3Mixing uniformly, wherein LiF-H3BO3LiF and H in the system3BO3The molar ratio of (1: 3), heating to 780 ℃ at the heating rate of 25 ℃/h, keeping the temperature for 40 hours, and then cooling to 680 ℃ to obtain a mixed melt;
preparing zinc calcium borate seed crystals: slowly cooling the obtained mixed solution to room temperature at the speed of 5 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
fixing the obtained seed crystal on a seed crystal rod, feeding the seed crystal from the top of a crystal growth furnace, preheating the seed crystal for 35 minutes, feeding the seed crystal into the mixed melt for remelting, keeping the temperature for 35 minutes, and reducing the temperature to 650 ℃ at a rate of 30 ℃/h;
slowly cooling at the speed of 2 ℃/day, rotating the seed rod at the rotating speed of 35rpm to grow crystals, lifting the crystals away from the surface of the mixed melt after the single crystals grow to the required size, cooling to room temperature at the speed of 55 ℃/h, and taking out the crystals from a hearth to obtain the calcium zinc borate nonlinear optical crystals with the size of 21mm multiplied by 14mm multiplied by 9 mm.
Example 19
According to the reaction formula: ca (OH)2+2ZnCO3+B2O3→CaZn2(BO3)2+2H2O↑+2CO2Preparation of CaZn from ↓2(BO3)2Nonlinear optical crystal:
directly adding Ca (OH) according to the molar ratio of 1:2:1:32，ZnCO3，B2O3The fluxing agent is LiF-NaF-H3BO3Mixing uniformly, wherein LiF-NaF-H3BO3LiF, NaF and H in the system3BO3The molar ratio of (1) to (3: 3: 1), heating to 690 ℃ at the heating rate of 18 ℃/h, keeping the temperature for 65 hours, and then cooling to 670 ℃ to obtain a mixed melt;
preparing zinc calcium borate seed crystals: slowly cooling the obtained mixed solution to room temperature at the speed of 6 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
fixing the obtained seed crystal on a seed crystal rod, feeding the seed crystal from the top of a crystal growth furnace, preheating the seed crystal for 55 minutes, feeding the seed crystal to the surface contacting with the mixed melt for remelting, keeping the temperature for 30 minutes, and reducing the temperature to 625 ℃ at the rate of 45 ℃/h;
and slowly cooling at the speed of 3 ℃/day, rotating the seed rod at the rotating speed of 5rpm to grow crystals, lifting the crystals away from the surface of the mixed melt after the single crystals grow to the required size, cooling to room temperature at the speed of 15 ℃/h, and taking the crystals out of the hearth to obtain the zinc calcium borate nonlinear optical crystals with the size of 20mm multiplied by 12mm multiplied by 8 mm.
Example 20
According to the reaction formula: ca (NO)3)2+2Zn(NO3)2+2H3BO3→CaZn2(BO3)2+6NO2↑+3H2O ↓ [ O ] preparation CaZn2(BO3)2Nonlinear optical crystal:
directly adding Ca (NO) according to the molar ratio of 1:2:2:13)2，Zn(NO3)2，H3BO3The fluxing agent is LiF-PbF2Mixing uniformly, wherein LiF-PbF2LiF and PbF in the system2The molar ratio of (1) to (3), heating to 660 ℃ at the heating rate of 30 ℃/h, keeping the temperature for 15 hours, and then cooling to 650 ℃ to obtain a mixed melt;
preparing zinc calcium borate seed crystals: slowly cooling the obtained mixed solution to room temperature at the speed of 0.5 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
fixing the obtained seed crystal on a seed crystal rod, feeding the seed crystal from the top of a crystal growth furnace, preheating the seed crystal for 5 minutes, feeding the seed crystal into the mixed melt for remelting, keeping the temperature for 60 minutes, and reducing the temperature to 620 ℃ at the rate of 30 ℃/h;
slowly cooling at the speed of 0.1 ℃/day, rotating the seed rod at the rotating speed of 1rpm to grow crystals, lifting the crystals away from the surface of the mixed melt after the single crystals grow to the required size, cooling to room temperature at the speed of 10 ℃/h, and taking out the crystals from a hearth to obtain the calcium zinc borate nonlinear optical crystals with the size of 22mm multiplied by 12mm multiplied by 10 mm.
Example 21
According to the reaction formula: CaCO3+2Zn(NO3)2+2H3BO3→CaZn2(BO3)2+CO2↑+3H2O↑+4NO2Preparation of CaZn from ↓2(BO3)2Nonlinear optical crystal:
CaCO is directly added according to the molar ratio of 1:2:2:13，Zn(NO3)2，H3BO3With fluxing agent CaF2Uniformly mixing, heating to 1000 ℃ at the heating rate of 1 ℃/h, keeping the temperature for 5 hours, and then cooling to 850 ℃ to obtain a mixed melt;
preparing zinc calcium borate seed crystals: c, slowly cooling the mixed solution obtained in the step b to room temperature at the speed of 0.5 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
fixing the obtained seed crystal on a seed crystal rod, feeding the seed crystal from the top of a crystal growth furnace, preheating the seed crystal for 5 minutes, feeding the seed crystal to the surface contacting with the mixed melt for remelting, keeping the temperature for 5 minutes, and reducing the temperature to 830 ℃ at the rate of 1 ℃/h;
slowly cooling at the speed of 0.1 ℃/day, rotating the seed rod at the rotating speed of 1rpm to grow crystals, lifting the crystals away from the surface of the mixed melt after the single crystals grow to the required size, cooling to room temperature at the speed of 10 ℃/h, and taking out the crystals from a hearth to obtain the calcium zinc borate nonlinear optical crystals with the size of 19mm multiplied by 16mm multiplied by 11 mm.
Example 22
Any CaZn obtained in examples 1 to 212(BO3)2A frequency doubling device with the size of 5mm multiplied by 6mm is processed by a nonlinear optical crystal according to the matching direction, the frequency doubling device is arranged at the position 3 according to the figure 3, a Q-switched Nd YAG laser is used as a light source at room temperature, the incident wavelength is 1064nm, an infrared beam 2 with the wavelength of 1064nm is emitted by the Q-switched Nd YAG laser 1 and is emitted into CaZn2(BO3)2A single crystal 3 for generating a green frequency-doubled light with a wavelength of 532nm, an output intensity of 3-4 times that of KDP under the same conditions, and an emergent light beam 4 containing infrared light with a wavelength of 1064nmThe light and the green light of 532nm are filtered by a filter 5 to obtain the green laser with the wavelength of 532 nm.
Claims (5)
1. A compound calcium zinc borate is characterized in that the chemical formula of the compound is CaZn2(BO3)2Molecular weight 288.44, compound was synthesized by solid phase reaction.
2. A calcium zinc borate nonlinear optical crystal is characterized in that the chemical formula of the crystal is CaZn2(BO3)2Molecular weight 288.44, not having a center of symmetry, belongs to the orthorhombic system, space groupAba2 (No. 33)Unit cell parameters a =11.7579(7) a, b =8.5721(4) a, c =4.9421(3) a, Z =4, V =498.11(5) a3。
3. The method for preparing the calcium zinc borate nonlinear optical crystal according to claim 2, characterized in that the crystal is grown by a high-temperature melt method, and the specific operation is carried out according to the following steps:
a. the calcium-containing compound is CaCO3、Ca(NO3)2Or Ca (OH)2(ii) a The zinc-containing compound is ZnO or ZnCO3、Zn(NO3)2Or Zn (OH)2(ii) a The boron-containing compound is H3BO3Or B2O3Weighing and placing the materials into a mortar according to the molar ratio of 1:2:2, mixing and carefully grinding the materials, then placing the materials into an open corundum crucible with the diameter of 100mm multiplied by 100mm, placing the mixture into a muffle furnace, slowly heating the mixture to 600 ℃, keeping the temperature for 24 hours, cooling the mixture to room temperature, taking the mixture out, placing the mixture into the muffle furnace after the second grinding, heating the mixture to 650 ℃, keeping the temperature for 24 hours, cooling the mixture to room temperature, taking the mixture out, placing the mixture into the muffle furnace after the third grinding, heating the mixture to 850 ℃, keeping the temperature for 48 hours, taking the mixture out, grinding the mixture to obtain single-phase polycrystalline powder of a zinc borate calcium compound, performing X-ray analysis on the single-phase polycrystalline powder, and performing X-ray analysis on the obtained X-ray spectrogram and calcium zinc borate CaZn2(BO3)2The X-ray spectrograms obtained from the single crystal structures are consistent;
b. b, mixing the polycrystalline powder obtained in the step a according to a molar ratio of 1:1-3The end and fluxing agent are CaF2、LiF、PbF2、LiF-H3BO3、LiF-NaF-H3BO3Or LiF-PbF2Uniformly mixing, heating to the temperature of 900-;
or directly using calcium-containing compound as CaCO3、Ca(NO3)2Or Ca (OH)2(ii) a The zinc-containing compound is ZnO or ZnCO3、Zn(NO3)2Or Zn (OH); the boron-containing compound is H3BO3Or B2O3With fluxing agent CaF2、LiF、PbF2、LiF-H3BO3、LiF-NaF-H3BO3Or LiF-PbF2Uniformly mixing the raw materials according to a molar ratio of 1:2:2:1-3, heating the mixture to 800 ℃ at a heating rate of 1-30 ℃/h, keeping the temperature for 5-80 hours, and cooling the mixture to 700 ℃ at 620 ℃ to obtain a mixed solution;
c. preparing zinc calcium borate seed crystals: b, slowly cooling the mixed solution obtained in the step b to room temperature at the speed of 0.5-10 ℃/h, and spontaneously crystallizing to obtain zinc calcium borate seed crystals;
d. c, fixing the seed crystal obtained in the step c on a seed crystal rod, lowering the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 5-60 minutes, lowering the seed crystal to the surface of the mixed melt or into the mixed melt for remelting, keeping the temperature for 5-60 minutes, and reducing the temperature to 620-700 ℃ at the speed of 1-60 ℃/h;
e. slowly cooling at the speed of 0.1-3 ℃/day, rotating the seed rod at the rotating speed of 1-60rpm to grow crystals, lifting the crystals away from the surface of the mixed melt after the single crystals grow to the required size, cooling to room temperature at the speed of 10-80 ℃/h, and taking out the crystals from a hearth to obtain the calcium zinc borate nonlinear optical crystals.
4. The method for preparing a compound calcium zinc borate nonlinear optical crystal according to claim 3, characterized in that in step b, the flux LiF-H3BO3LiF and H in the system3BO3The molar ratio of (A) to (B) is 1: 1-3; LiF-PbF2LiF and PbF in the system2Mole ofThe ratio is 2-3: 1; LiF-NaF-H3BO3LiF, NaF and H in the system3BO3The molar ratio of (A) to (B) is 1-3:1-3: 1.
5. Use of the zinc calcium borate nonlinear optical crystal of claim 2 in the preparation of a frequency doubling generator, an upper frequency converter, a lower frequency converter, or an optical parametric oscillator.
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| PCT/CN2022/125404 WO2023109293A1 (en) | 2021-12-16 | 2022-10-14 | Zinc calcium borate compound and zinc calcium borate nonlinear optical crystal, preparation method therefor, and use thereof |
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| CN115504480A (en) * | 2022-09-21 | 2022-12-23 | 中国科学院新疆理化技术研究所 | Compound zinc barium borate and zinc barium borate birefringent crystal, and preparation method and application thereof |
| WO2023109293A1 (en) * | 2021-12-16 | 2023-06-22 | 中国科学院新疆理化技术研究所 | Zinc calcium borate compound and zinc calcium borate nonlinear optical crystal, preparation method therefor, and use thereof |
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| CN103590107B (en) * | 2012-08-17 | 2016-01-20 | 中国科学院新疆理化技术研究所 | Boronic acid compound caesium zinc and boric acid caesium zinc non-linear optic crystal and Preparation method and use |
| CN103803572B (en) * | 2012-11-13 | 2016-01-20 | 中国科学院新疆理化技术研究所 | Compound lithium-fluoroborate calcium and lithium-fluoroborate calcium non-linear optical crystal and preparation method and purposes |
| CN106283192B (en) * | 2015-05-27 | 2018-08-17 | 中国科学院新疆理化技术研究所 | Compound lead barium zinc boron oxygen and lead barium zinc boron oxygen nonlinear optical crystal and preparation method and purposes |
| CN107699948B (en) * | 2017-09-08 | 2019-07-19 | 中国科学院新疆理化技术研究所 | Serial composition metal RE borate and composition metal RE borate nonlinear optical crystal and preparation method and purposes |
| CN114232093B (en) * | 2021-12-16 | 2024-01-05 | 中国科学院新疆理化技术研究所 | Compound zinc calcium borate and zinc calcium borate nonlinear optical crystal, preparation method and application |
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Non-Patent Citations (1)
| Title |
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| ROBERT W. SMITH等: "The Noncentrosymmetric OrthoborateBaZn2(BO3)2", JOURNAL OF SOLID STATE CHEMISTRY, vol. 100, pages 325 - 330 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023109293A1 (en) * | 2021-12-16 | 2023-06-22 | 中国科学院新疆理化技术研究所 | Zinc calcium borate compound and zinc calcium borate nonlinear optical crystal, preparation method therefor, and use thereof |
| CN115504480A (en) * | 2022-09-21 | 2022-12-23 | 中国科学院新疆理化技术研究所 | Compound zinc barium borate and zinc barium borate birefringent crystal, and preparation method and application thereof |
| CN115504480B (en) * | 2022-09-21 | 2024-03-01 | 中国科学院新疆理化技术研究所 | Compound zinc barium borate and zinc barium borate birefringent crystal, and preparation method and application thereof |
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