CN112575374A - Compound cesium chlorofluorocarbonboron zincate and cesium chlorofluorocarbonboron zincate nonlinear optical crystal as well as preparation method and application thereof - Google Patents

Compound cesium chlorofluorocarbonboron zincate and cesium chlorofluorocarbonboron zincate nonlinear optical crystal as well as preparation method and application thereof Download PDF

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CN112575374A
CN112575374A CN201910942723.6A CN201910942723A CN112575374A CN 112575374 A CN112575374 A CN 112575374A CN 201910942723 A CN201910942723 A CN 201910942723A CN 112575374 A CN112575374 A CN 112575374A
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cesium
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zincate
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俞洪伟
周金杰
吴红萍
胡章贵
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Tianjin University of Technology
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Abstract

Compound cesium chlorofluorocarbon zincate and cesium chlorofluorocarbon zincate nonlinear optical crystals and preparation method and application thereof, wherein chemical formulas of the compound cesium chlorofluorocarbon zincate and the cesium chlorofluorocarbon zincate nonlinear optical crystals are CsZn2BO3FCl, crystal belongs to trigonal system, space group R32, unit cell parameter is
Figure DDA0002223352150000011
Molecular weight of 376.90, and its powder frequency doubling effect is about 2.3 times KDP (KH)2PO4). The compound cesium chlorofluorocarbonzincate is synthesized by a solid-phase reaction method, a cesium chlorofluorocarbonzincate nonlinear optical crystal grows by a high-temperature melt method or a Czochralski method, and the ultraviolet absorption cut-off edge of the cesium chlorofluorocarbonzincate nonlinear optical crystal is less than 200 nm. The method is widely applied to preparation of ultraviolet-deep ultraviolet nonlinear optical devices such as a frequency doubling generator, an upper frequency converter, a lower frequency converter or an optical parametric oscillator.

Description

Compound cesium chlorofluorocarbonboron zincate and cesium chlorofluorocarbonboron zincate nonlinear optical crystal as well as preparation method and application thereof
Technical Field
The invention relates to a chemical formula CsZn2BO3FCl cesium chlorofluorocarbonzincate and cesium chlorofluorocarbonzincate nonlinear optical crystals, a preparation method of the crystals and a nonlinear optical device manufactured by using the crystals.
Background
The exploration of a novel nonlinear optical crystal with large frequency doubling effect, wide transmission waveband, large optical damage threshold and stable physical and chemical properties is always a hot topic in the field of laser frequency conversion. The main nonlinear optical materials at present are: beta-BaB2O4(BBO) Crystal, LiB3O5(LBO) crystal, CsB3O5(CBO) crystal, CsLiB6O10(CLBO) Crystal and KBe2BO3F2(KBBF) crystal. Although the crystal growth techniques for these materials are becoming more sophisticated, there are still significant disadvantages: such as easy deliquescence of crystal, long growth period, serious lamellar growth habit, high price and the like. Therefore, finding new nonlinear optical crystal materials remains a very important and difficult task. In order to make up for the above shortcomings of nonlinear optical crystals, scientists in various countries still pay great attention to the exploration and research of various novel nonlinear optical crystals, not only pay attention to the optical properties and mechanical properties of the crystals, but also pay more and more attention to the preparation characteristics of the crystals.
The borate crystal is an important ultraviolet-deep ultraviolet nonlinear optical material, has widely concerned performance, and has wider application in the fields of optics, military exploration, laser medical treatment and the like. The band gap is larger, the laser damage threshold is higher, the physical and chemical properties are stable, the stronger nonlinear optical effect is favorably obtained, the method is an ideal selection of a novel ultraviolet nonlinear optical crystal, and alkali metal cations (Cs) are introduced into borate, so that d-d electronic transition is avoided, and the method is an ideal selection of ultraviolet region transmission. Therefore, the synthesis of the alkali metal borate is an effective means for designing the ultraviolet nonlinear optical material with large frequency doubling effect.
Disclosure of Invention
The invention aims to provide a compound cesium chlorofluorocarbonate zincate and a cesium chlorofluorocarbonate zincate nonlinear optical crystal, wherein the chemical formulas of the cesium chlorofluorocarbonate zincate and the cesium chlorofluorocarbonate zincate are CsZn2BO3FCl；
The invention also aims to provide a preparation method for synthesizing the compound cesium fluorochloroboron zincate by adopting a solid-phase reaction method and growing the cesium fluorochloroboron zincate nonlinear optical crystal by adopting a high-temperature melt method or a pulling method;
it is a further object of the present invention to provide the use of cesium fluorochloroborozincate nonlinear optical devices for the preparation of frequency doublers, upper or lower frequency converters or optical parametric oscillators.
The technical scheme of the invention is as follows:
the chemical formula of the compound cesium fluorochloroborozincate provided by the invention is CsZn2BO3FCl, respectively; the preparation process comprises the following steps: uniformly mixing raw materials of a cesium-containing compound, a zinc-containing compound, a boron-containing compound, a fluorine-containing compound and a chlorine-containing compound, grinding, putting into a muffle furnace, pre-burning to remove moisture and gas in the raw materials, cooling to room temperature, taking out, grinding, putting into the muffle furnace, and calcining to obtain a compound cesium chlorofluorocarbonyl zincate;
the cesium-containing compound comprises at least one of cesium hydroxide, cesium oxide and cesium salt; the cesium salt includes at least one of cesium fluoride, cesium chloride, cesium bromide, cesium nitrate, cesium oxalate, cesium carbonate, cesium bicarbonate, and cesium sulfate;
the zinc-containing compound comprises at least one of zinc oxide, zinc hydroxide and zinc salt; the zinc salt comprises at least one of zinc fluoride, zinc chloride, zinc bromide, zinc nitrate, zinc oxalate, zinc carbonate, zinc bicarbonate and zinc sulfate;
the boron-containing compound is at least one of boron oxide and boric acid;
the chlorine-containing compound comprises at least one of zinc chloride, cesium chloride, lithium chloride, sodium chloride, potassium chloride and rubidium chloride;
the chlorine-containing compound comprises at least one of zinc fluoride, cesium fluoride, lithium fluoride, sodium fluoride, potassium fluoride and rubidium fluoride;
the solid-phase reaction method is adopted to prepare the chlorofluoboric zinc cesium compound according to the following chemical reaction formula:
1)Cs2CO3+2ZnCl2+2ZnF2+2H3BO3→2CsZn2BO3FCl+CO2↑+2H2O↑
2)2CsNO3+2ZnCl2+2ZnF2+B2O3→2CsZn2BO3FCl+2NO2↑
3)2CsOH+2ZnCl2+2ZnF2+B2O3→2CsZn2BO3FCl+H2O↑
4)Cs2SO4+2ZnCl2+2ZnF2+B2O3→2CsZn2BO3FCl+SO2↑+O2↑
5)2CsCl+2ZnCl2+2ZnF2+B2O3→2CsZn2BO3FCl+Cl2↑
6)2CsBr+2ZnCl2+2ZnF2+B2O3→2CsZn2BO3FCl+Br2↑
7)Cs2O+2ZnCl2+2ZnF2+B2O3→2CsZn2BO3FCl
8)2CsHCO3+2ZnCl2+2ZnF2+B2O3→2CsZn2BO3FCl+2CO2↑+H2O↑
9)2CsF+2ZnCl2+2ZnF2+B2O3→2CsZn2BO3FCl+3F2↑
10)2CsCl+2CsF+4ZnO+B2O3→2CsZn2BO3FCl+O2↑
the cesium fluorochloroborozincate nonlinear optical crystal provided by the invention is characterized in that the chemical formula of the crystal is CsZn2BO3FCl, crystal belongs to trigonal system, space group R32, unit cell parameter is
Figure BDA0002223352130000031
Molecular weight of 376.90, and its powder frequency doubling effect is about 2.3 times KDP (KH)2PO4)。
The invention provides a preparation method of a cesium chlorofluorocarbon zincate nonlinear optical crystal, which adopts a high-temperature melt method or a pulling method to grow the cesium chlorofluorocarbon zincate nonlinear optical crystal and specifically comprises the following steps:
a. uniformly mixing the compound cesium fluorochloroborozincate single-phase polycrystalline powder with a fluxing agent, heating the mixture to the temperature of 500-650 ℃ at the heating rate of 1-30 ℃/h, keeping the temperature for 5-80 hours to obtain a mixed melt, and cooling to the temperature of 450-580 ℃, wherein the molar ratio of the compound cesium fluorochloroborozincate single-phase polycrystalline powder to the fluxing agent is 1: 0-20;
or directly heating a mixture of a cesium-containing compound, a zinc-containing compound and a boron-containing compound or a mixture of the cesium-containing compound, the zinc-containing compound, the boron-containing compound, the fluorine-containing compound and a chlorine-containing compound with a fluxing agent at the temperature rise rate of 1-30 ℃/h to the temperature of 500-650 ℃, keeping the temperature for 5-80 hours to obtain a mixed melt, and then cooling to the temperature of 450-580 ℃, wherein the molar ratio of the cesium-containing compound, the zinc-containing compound, the boron-containing compound, the fluorine-containing compound, the chlorine-containing compound and the fluxing agent is 1:2:1:1: 0-20;
the fluxing agent being predominantly a self fluxing agent, such as Cs2CO3、CsF、CsOH、Cs2O、CsCl、ZnO、ZnF2、ZnCl2、H3BO3、B2O3Etc. and other complex fluxes, e.g. Cs2CO3-B2O3、Cs2CO3-ZnO、Cs2O-ZnCl2、Cs2O-B2O3、CsF-B2O3、CsCl-B2O3、CsCl-ZnCl2、Cs2O-ZnO、Cs2CO3-MoO3、CsCl-MoO3、CsCl-TeO2、B2O3-TeO2、CsCl-Cs2CO3、PbO-PbF2、Li2O-PbO、RbCl-PbF2、MoO3-PbF2、ZnO-B2O3、CsF-CsCl-B2O3、ZnO-B2O3-Cs2O, and the like.
The compound cesium chlorofluorocarbonzincate single-phase polycrystalline powder is prepared by a solid-phase synthesis method, and comprises the following steps: the preparation method comprises the steps of mixing a cesium-containing compound, a zinc-containing compound, a boron-containing compound, a fluorine-containing compound and a chlorine-containing compound to prepare the compound cesium chlorofluoro zincate by a solid-phase reaction method, wherein the molar ratio of element cesium in the cesium-containing compound, element zinc in the zinc-containing compound, element boron in the boron-containing compound, element fluorine in the fluorine-containing compound and element chlorine in the chlorine-containing compound is 1:2:1:1:1, uniformly mixing the cesium-containing compound, the zinc-containing compound, the boron-containing compound and the chlorine-containing compound, grinding, putting into a muffle furnace, pre-burning to remove moisture and gas in the raw materials, cooling to room temperature, taking out and grinding, putting into the muffle furnace for calcination, heating to 650 ℃, keeping the temperature for 72 hours, cooling to room temperature, taking out and grinding to prepare the compound cesium.
b. Preparing a fluorine chloro boron cesium zincate seed crystal: slowly cooling the mixed solution obtained in the step a to room temperature at the speed of 0.5-10 ℃/h, and spontaneously crystallizing to obtain the cesium fluorochloroborozincate seed crystal;
c. b, placing the crucible containing the mixed melt prepared in the step a into a crystal growth furnace, fixing the seed crystal obtained in the step b on a seed crystal rod, preheating the seed crystal from the top of the crystal growth furnace for 5-60 minutes, placing the seed crystal until the seed crystal is in contact with the liquid level of the mixed melt or the mixed melt for remelting, keeping the temperature for 5-60 minutes, and reducing the temperature to the saturation temperature at the rate of 1-60 ℃/h;
d. and slowly cooling at the speed of 0.1-5 ℃/day, rotating the seed crystal rod at the rotating speed of 0-60rpm to grow crystals, lifting the crystals away from the surface of the mixed melt after the single crystals grow to the required size, cooling to room temperature at the speed of 1-80 ℃/h, and taking out the crystals from a hearth to obtain the cesium fluorochloroborozincate nonlinear optical crystal.
The fluxing agent is compounded with the fluxing agent Cs2O-B2O3Cs in the system2O and B2O3The molar ratio of (A) to (B) is 1-5: 2-7; cs2Cs in O-PbO system2The molar ratio of O to PbO is 1-5: 3-7; MoO3-PbF2MoO in the system3And PbF2The molar ratio of (A) to (B) is 1-2: 2-7; PbO-PbF2In the system of PbO and PbF2The molar ratio is 1-5: 1-5; ZnO-B2O3ZnO and B in the system2O3The molar ratio is 1-7: 3-8; ZnO-B2O3-Cs2ZnO and Cs in O system2O and B2O3The molar ratio is 2-6:1-7: 4-8.
The cesium fluorochloroborozincate nonlinear optical crystal prepared by the invention is characterized in that the chemical formula of the crystal is CsZn2BO3FCl, crystal belongs to trigonal system, space group R32, unit cell parameter is
Figure BDA0002223352130000051
Molecular weight of 376.90, and its powder frequency doubling effect is about 2.3 times KDP (KH)2PO4)。
Because of the use of, for example, Cs in the growth of cesium fluorochloroborozincate nonlinear optical crystals2CO3、CsF、CsOH、Cs2O、CsCl、ZnO、ZnF2、ZnCl2、H3BO3、B2O3Etc. and other complex fluxes, e.g. Cs2CO3-B2O3、Cs2CO3-ZnO、Cs2O-ZnCl2、Cs2O-B2O3、CsF-B2O3、CsCl-B2O3、CsCl-ZnCl2、Cs2O-ZnO、Cs2CO3-MoO3、CsCl-MoO3、CsCl-TeO2、B2O3-TeO2、CsCl-Cs2CO3、PbO-PbF2、Li2O-PbO、RbCl-PbF2、MoO3-PbF2、ZnO-B2O3、ZnO-B2O3-Cs2O and other composite cosolvents, the product purity is high, the crystal is easy to grow and is transparent and free of wrapping, and the crystal growth method has the advantages of high growth speed, low cost, easy obtainment of large-size crystals and the like; the obtained crystal has the advantages of wider light-transmitting wave band, higher hardness, good mechanical property, difficult cracking and deliquescence, easy processing and storage and the like. The nonlinear optical device prepared by the compound cesium fluorochloroborozincate nonlinear optical crystal obtained by the method uses an Nd-YAG Q-switched laser as a light source at room temperature, emits 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) 2.3 times of the total weight of the powder.
Drawings
FIG. 1 shows CsZn of the present invention2BO3FCl powder, and its x-ray diffraction pattern.
FIG. 2 shows CsZn of the present invention2BO3FCl working principle diagram of nonlinear optical device made of crystal, wherein 1 is laser, 2 is emitted light beam, and 3 is CsZn2BO3FCl crystal, 4 outgoing beam and 5 filter.
Detailed Description
The invention is described in detail below with reference to the following figures and examples:
example 1:
according to the reaction formula: cs2CO3+2ZnCl2+2ZnF2+2H3BO3→2CsZn2BO3FCl+CO2↑+2H2O ↓syntheticcompound CsZn2BO3FCl：
Mixing Cs2CO3、ZnCl2、ZnF2、H3BO3Weighing and placing the materials into a mortar according to the mol ratio of 1:2:2:2, 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 300 ℃, 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 550 ℃, 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, keeping the temperature for 48 hours at 550 ℃, taking the mixture out, and grinding the mixture to obtainCompound cesium chlorofluorocarbonzincate single-phase polycrystalline powder is subjected to X-ray analysis, and an obtained X-ray spectrogram and cesium chlorofluorocarbonzincate CsZn are obtained2BO3FCl the X-ray spectra obtained for the single crystal structure are consistent;
the obtained compound of cesium fluorochloroborozincate CsZn2BO3FCl Single-phase polycrystalline powder and flux Cs2O-B2O3In molar ratio CsZn2BO3FCl:Cs2O-B2O31:4, wherein Cs2O and B2O3The molar ratio of the components is 3:5, the mixture is mixed and loaded into an opening platinum crucible with the diameter phi of 80mm multiplied by 80mm, the mixture is heated to 600 ℃ at the heating rate of 30 ℃/h and is kept at the constant temperature for 15 hours to obtain a mixed melt, and then the temperature is reduced to 580 ℃;
slowly cooling to room temperature at the speed of 1 ℃/h, and spontaneously crystallizing to obtain the cesium fluorochloroborozincate seed crystal;
growing crystals in a compound melt: CsZn to be obtained2BO3FCl seed crystal is fixed on the seed crystal rod, the seed crystal is placed from the top of the crystal growth furnace, the seed crystal is preheated on the surface of the mixed melt for 10 minutes, and then is immersed in the liquid surface, so that the seed crystal is melted back in the mixed melt, the temperature is kept for 30 minutes, and the temperature is rapidly reduced to the saturation temperature 580 ℃;
cooling at a rate of 1 ℃/day, rotating the seed rod at a rotating speed of 7rpm, separating the crystal from the liquid surface after the crystal growth is finished, and cooling to room temperature at a rate of 10 ℃/hour to obtain CsZn with the size of 12mm multiplied by 13mm multiplied by 3mm2BO3FCl crystal.
Example 2:
according to the reaction formula: 2CsNO3+2ZnCl2+2ZnF2+B2O3→2CsZn2BO3FCl+2NO2↑
Synthesis of Compound CsZn2BO3FCl：
CsNO is added3、ZnCl2、ZnF2、H3BO3Directly weighing raw materials according to the mol ratio of 2:2:2:1, and mixing the weighed raw materials with a fluxing agent Cs2Mixing O-PbO according to the molar ratio of 1:4In which Cs2The molar ratio of O to PbO is 2:4, the mixture is put into an open platinum crucible with the diameter of 80mm multiplied by 80mm, the temperature is raised to 630 ℃, the temperature is kept for 60 hours, mixed melt is obtained, and the temperature is cooled to 540 ℃;
slowly cooling to room temperature at the speed of 1.5 ℃/h, and spontaneously crystallizing to obtain the cesium fluorochloroborozincate seed crystal;
CsZn to be obtained2BO3FCl seed crystal is fixed on the seed crystal rod and is dropped from the top of the crystal growing furnace, the seed crystal is preheated on the surface of the mixed melt for 10 minutes, and is immersed under the liquid surface, so that the seed crystal is melted back in the mixed melt, the temperature is kept for 30 minutes, and the temperature is rapidly reduced to the saturation temperature of 540 ℃;
slowly cooling at the speed of 1 ℃/day without rotating a seed rod, lifting the crystal away from the surface of the melt after the crystal grows to the required size, cooling to room temperature at the speed of 25 ℃/h, and taking out the crystal from a hearth to obtain CsZn with the size of 9mm multiplied by 8mm multiplied by 1.5mm2BO3FCl crystal.
Example 3:
according to the reaction formula: 2CsOH +2ZnCl2+2ZnF2+B2O3→2CsZn2BO3FCl+H2O ↓syntheticcompound CsZn2BO3FCl：
Mixing CsOH and ZnCl2、ZnF2、H3BO3Directly weighing raw materials according to the mol ratio of 2:2:2:1, and mixing the weighed raw materials with a fluxing agent ZnO-B2O3Mixing according to a molar ratio of 1:2, wherein ZnO and B are mixed2O3The molar ratio is 5:4, the mixture is put into an opening platinum crucible with the diameter of 80mm multiplied by 80mm, the temperature is raised to 650 ℃, the temperature is kept for 60 hours, mixed melt is obtained, and the temperature is lowered to 500 ℃;
slowly cooling to room temperature at the speed of 7 ℃/h, and spontaneously crystallizing to obtain the cesium fluorochloroborozincate seed crystal;
CsZn to be obtained2BO3FCl seed crystal is fixed on the seed crystal rod and is placed from the top of the crystal growing furnace, the seed crystal is preheated on the surface of the mixed melt for 15 minutes and immersed under the liquid surface to melt back the seed crystal in the mixed melt, and the temperature is constantRapidly cooling to the saturation temperature of 500 ℃ for 30 minutes;
slowly cooling at the speed of 3 ℃/day, rotating the seed crystal crucible at the rotating speed of 10rpm, lifting the crystal from the surface of the melt after the crystal grows to the required size, cooling to room temperature at the speed of 1 ℃/h, and taking out the crystal from the hearth to obtain CsZn with the size of 12mm multiplied by 7mm multiplied by 2mm2BO3FCl crystal.
Example 4:
according to the reaction formula: 2CsCl +2ZnCl2+2ZnF2+B2O3→2CsZn2BO3FCl+Cl2↓ [ synthetic compound CsZn2BO3FCl：
Mixing CsCl and ZnCl2、ZnF2、H3BO3Directly weighing raw materials according to the mol ratio of 2:2:2:1, and mixing the weighed raw materials with a fluxing agent PbF2-PbO is mixed according to a molar ratio of 1:7, wherein PbF2The molar ratio of the raw material to PbO is 1:1, the raw material is put into an opening platinum crucible with the diameter of 80mm multiplied by 80mm, the temperature is raised to 600 ℃, the temperature is kept for 80 hours, mixed melt is obtained, and the temperature is reduced to 530 ℃;
slowly cooling to room temperature at the speed of 4 ℃/h, and spontaneously crystallizing to obtain the cesium fluorochloroborozincate seed crystal;
CsZn to be obtained2BO3FCl seed crystal is fixed on the seed crystal rod and is placed from the top of the crystal growing furnace, the seed crystal is preheated on the surface of the mixed melt for 20 minutes and is immersed under the liquid surface, the seed crystal is melted back in the mixed melt, the temperature is kept for 5 minutes, and the temperature is rapidly reduced to 530 ℃ of saturation temperature;
then slowly cooling at the speed of 3 ℃/day, rotating the seed rod at the rotating speed of 7rpm, separating the crystal body from the surface of the melt after the crystal grows to the required size, cooling to room temperature at the speed of 14 ℃/h, and taking out the crystal from the hearth to obtain the CsZn with the size of 15mm multiplied by 9mm multiplied by 2.5mm2BO3FCl crystal.
Example 5
According to the reaction formula: cs2O+2ZnCl2+2ZnF2+B2O3→2CsZn2BO3FCl alloyCompound CsZn2BO3FCl：
Mixing Cs2O、ZnCl2、ZnF2、H3BO3Directly weighing raw materials according to the mol ratio of 1:2:2:1, and mixing the weighed raw materials with a fluxing agent PbF2-PbO is mixed according to a molar ratio of 1:3, wherein PbF2Loading the mixture into an opening platinum crucible with phi 80mm multiplied by 80mm and the molar ratio of the mixture to PbO being 4:5, heating to 630 ℃, keeping the temperature for 80 hours to obtain a mixed solution, and cooling to 500 ℃;
slowly cooling to room temperature at the speed of 8 ℃/h, and spontaneously crystallizing to obtain the cesium fluorochloroborozincate seed crystal;
CsZn to be obtained2BO3FCl seed crystal is fixed on the seed crystal rod and is placed from the top of the crystal growing furnace, the seed crystal is preheated on the surface of the mixed melt for 25 minutes, and is partially immersed under the liquid surface, so that the seed crystal is melted back in the mixed melt, the temperature is kept for 25 minutes, and the temperature is rapidly reduced to 500 ℃ of saturation temperature;
cooling at the speed of 5 ℃/day, rotating the seed rod at the rotating speed of 10rpm, lifting the crystal from the surface of the melt after the crystal grows to the required size, cooling to room temperature at the speed of 15 ℃/h, and taking out the crystal from the hearth to obtain CsZn with the size of 12mm multiplied by 5mm multiplied by 2mm2BO3FCl crystal.
Example 6
CsZn obtained in examples 1 to 52BO3FCl A frequency multiplier with 5mm × 5mm × 2mm size is processed by crystal along matching direction, and is arranged at 3 position as shown in FIG. 2, at room temperature, a Q-switched Nd: YAG laser is used as light source with incident wavelength of 1064nm, and infrared beam 2 with wavelength of 1064nm emitted by the Q-switched Nd: YAG laser 1 is incident into CsZn2BO3 FCl Single crystal 3, generating a green frequency doubling light with wavelength of 532nm, the output intensity is 2.3 times of KDP under the same condition, the emergent light beam 4 contains infrared light with wavelength of 1064nm and green light with wavelength of 532nm, and the green laser with wavelength of 532nm is obtained after filtering by a filter 5.

Claims (9)

1. The compound of cesium chlorofluorocarbonzincate is characterized in that the compound of cesium chlorofluorocarbonzincateCesium of the formula CsZn2BO3FCl。
2. The method for preparing cesium fluorochloroborozincate according to claim 1, characterized by comprising the steps of: the method comprises the following steps of mixing a cesium-containing compound, a zinc-containing compound, a boron-containing compound, a fluorine-containing compound and a chlorine-containing compound to prepare the compound cesium chlorofluorocarbonzincate by adopting a solid-phase reaction method, wherein the molar ratio of element cesium in the cesium-containing compound, element zinc in the zinc-containing compound, element boron in the boron-containing compound, element fluorine in the fluorine-containing compound and element chlorine in the chlorine-containing compound is 1:2:1:1: 1.
3. The method for preparing cesium fluorochloroboron zincate as defined in claim 2, wherein said compound cesium fluorochloroboron zincate is prepared by a solid phase reaction method comprising: uniformly mixing raw materials of a cesium-containing compound, a zinc-containing compound, a boron-containing compound, a fluorine-containing compound and a chlorine-containing compound, grinding, putting into a muffle furnace, pre-burning to remove moisture and gas in the raw materials, cooling to room temperature, taking out, grinding, putting into the muffle furnace, and calcining to obtain a compound cesium chlorofluorocarbonyl zincate;
the cesium-containing compound comprises at least one of cesium hydroxide, cesium oxide and cesium salt; the cesium salt includes at least one of cesium fluoride, cesium chloride, cesium bromide, cesium nitrate, cesium oxalate, cesium carbonate, cesium bicarbonate, and cesium sulfate.
The zinc-containing compound comprises at least one of zinc oxide, zinc fluoride and zinc salt; the zinc salt comprises at least one of zinc fluoride, zinc chloride, zinc bromide, zinc nitrate, zinc oxalate, zinc carbonate, zinc bicarbonate and zinc sulfate;
the boron-containing compound is at least one of boron oxide and boric acid;
the chlorine-containing compound comprises at least one of zinc chloride, cesium chloride, lithium chloride, sodium chloride, potassium chloride and rubidium chloride;
the chlorine-containing compound comprises at least one of zinc fluoride, cesium fluoride, lithium fluoride, sodium fluoride, potassium fluoride and rubidium fluoride.
4. The compound cesium chlorofluorocarbonzincate and cesium chlorofluorocarbonzincate nonlinear optical crystal are characterized in that the chemical formula of the crystal is CsZn2BO3FCl, crystal belongs to trigonal system, space group R32, unit cell parameter is
Figure FDA0002223352120000021
Figure FDA0002223352120000022
5. The method for preparing cesium fluoroborozincate nonlinear optical crystals according to claim 4, wherein the cesium fluoroborozincate nonlinear optical crystals are grown by a high-temperature melt method or a Czochralski method.
6. The method as claimed in claim 5, wherein the noncrystalline optical crystal of cesium fluorochloroborozincate is prepared by a high temperature melt method or a Czochralski method, and the process comprises:
a. heating a mixture of the compound cesium fluorochloroboron zincate single-phase polycrystalline powder obtained in any one of claims 1 to 3 or the compound cesium fluorochloroboron zincate single-phase polycrystalline powder obtained in any one of claims 1 to 3 and a flux to melt to obtain a mixed melt;
or directly heating and melting a mixture of the cesium-containing compound, the zinc-containing compound, the boron-containing compound, the fluorine-containing compound and the chlorine-containing compound or a mixture of the cesium-containing compound, the zinc-containing compound, the boron-containing compound, the fluorine-containing compound, the chlorine-containing compound and a fluxing agent to obtain a mixed melt;
b. b, placing the crucible containing the mixed melt prepared in the step a into a crystal growth furnace, fixing seed crystals on a seed crystal rod, putting the seed crystals down to be in contact with the liquid level of the mixed melt or in the mixed melt for remelting, and reducing the temperature to saturation temperature; cooling or growing at constant temperature to prepare the fluorine chloro boron cesium zincate nonlinear optical crystal.
7. Root of herbaceous plantThe method of claim 6, wherein the molar ratio of the compound cesium fluorochloroborozincate single-phase polycrystalline powder to the flux is 1:0 to 20; or wherein the molar ratio of the cesium-containing compound, the zinc-containing compound, the boron-containing compound, the chlorine-containing compound and the fluorine-containing compound to the flux is 1:2:1:1:1: 0-20; the fluxing agent comprises at least one of cesium hydroxide, cesium fluoride, cesium chloride, zinc hydroxide, cesium oxide, zinc oxide, boron oxide, cesium salt, zinc salt and boron salt, lead oxide, molybdenum oxide, tellurium oxide, and a composite fluxing agent PbO-PbF2、Li2O-PbO、RbF-PbF2、MoO3-PbF2、ZnO-B2O3、ZnO-B2O3-Cs2And O is one or more.
8. The method of claim 7 wherein the composite flux Cs2O-B2O3Cs in the system2O and B2O3The molar ratio of (A) to (B) is 1-5: 2-7; cs2Cs in O-PbO system2The molar ratio of O to PbO is 1-5: 3-7; MoO3-PbF2MoO in the system3And PbF2The molar ratio of (A) to (B) is 1-2: 2-7; PbO-PbF2In the system of PbO and PbF2The molar ratio is 1-5: 1-5; ZnO-B2O3ZnO and B in the system2O3The molar ratio is 1-7: 3-8; ZnO-B2O3-Cs2ZnO and Cs in O system2O and B2O3The molar ratio is 2-6:1-7: 4-8.
9. Use of a cesium fluoroborozincate nonlinear optical crystal according to claim 4, characterized in that it is used to prepare a frequency doubler generator, an upper frequency converter, a lower frequency converter or an optical parametric oscillator.
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