WO2018184312A1 - 化合物氟硼酸铯和氟硼酸铯非线性光学晶体及制备方法和用途 - Google Patents

化合物氟硼酸铯和氟硼酸铯非线性光学晶体及制备方法和用途 Download PDF

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WO2018184312A1
WO2018184312A1 PCT/CN2017/092331 CN2017092331W WO2018184312A1 WO 2018184312 A1 WO2018184312 A1 WO 2018184312A1 CN 2017092331 W CN2017092331 W CN 2017092331W WO 2018184312 A1 WO2018184312 A1 WO 2018184312A1
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temperature
crystal
compound
csb
csbf
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潘世烈
王雪飞
张方方
王颖
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Definitions

  • the invention relates to a compound bismuth borofluoride CsB 4 O 6 F and a bismuth fluoroborate CsB 4 O 6 F nonlinear optical crystal, a preparation method and a use thereof.
  • nonlinear optical crystals As an important component of all-solid-state lasers, nonlinear optical crystals have been widely studied by scholars at home and abroad. After half a century of research, a series of nonlinear optical crystals with excellent performance have been discovered. Representative nonlinear optical crystals in the visible light band are KTiOPO 4 (KTP), KH 2 PO 4 (KDP) and the like. In the ultraviolet band, non-linear optical crystals such as LiB 3 O 5 (LBO), CsB 3 O 5 (CBO), CsLiB 6 O 10 (CLBO), and BaB 2 O 4 (BBO) have been industrialized. However, in the deep ultraviolet band of 200 nm or less, the practical nonlinear optical crystal is only KBe 2 BO 3 F 2 (KBBF). Due to the long growth cycle of the crystal, the highly toxic Be element, and the layered growth habit, the application is limited to some extent. Therefore, it is necessary to explore new deep ultraviolet nonlinear optical crystals with better performance.
  • KTP KH 2 PO 4
  • the invention invented the compound ammonium fluoroborate NH 4 B 4 O 6 F and ammonium fluoroborate NH 4 B 4 O 6 F nonlinear optical crystal, patent application number 201611128283.3, the invention and ammonium fluoroborate NH 4 the main difference between B 4 O 6 F lies, NH 4 B 4 O 6 F NH 4 + and the anionic group is hydrogen bonded, and CsB 4 O 6 F of Cs + ions to bond to anionic groups, resulting in The structure of the two, the growth habits are completely different, and the key parameters of the growth process, crystal properties, etc. are different from NH 4 B 4 O 6 F.
  • Still another object of the present invention is to provide a method for preparing a bismuth borofluoride CsB 4 O 6 F nonlinear optical crystal by using a melt method, a high temperature melt method, a vacuum encapsulation method, a hydrothermal method or a room temperature solution method to grow crystals.
  • Still another object of the present invention is to provide a use of a bismuth borofluoride CsB 4 O 6 F nonlinear optical crystal.
  • the compound of the present invention has a chemical formula of CsB 4 O 6 F and a molecular weight of 291.15.
  • the compound has a crystal structure.
  • the preparation method of the compound bismuth borofluoride is prepared by a solid phase synthesis method or a vacuum encapsulation method, and the specific operation is carried out according to the following steps:
  • the compound containing B is H 3 BO 3 , B 2 O 3 or CsBF 4 .
  • the temperature reaches 1 ⁇ 10 -3 Pa, is sealed at a high temperature, is placed in a muffle furnace, and is heated to 350-600 ° C at a rate of 10-50 ° C, and is heated at a constant temperature of 3-96 hours to obtain a compound CsB 4 O 6 F.
  • the Cs-containing compound is Cs 2 CO 3, CsNO 3, CsHCO 3, CsF or CsBF 4;
  • F-containing compound is CsF or CsBF 4;
  • B-containing compound is H 3 BO 3, B 2 O 3 or CsBF 4.
  • the preparation method of the bismuth borofluoride nonlinear optical crystal is formed by a melt method, a high temperature melt method, a vacuum encapsulation method, a hydrothermal method or a room temperature solution method;
  • the obtained compound CsB 4 O 6 F polycrystalline powder is placed in a cleaned platinum crucible, placed in a muffle furnace, and heated to a temperature of 400-700 ° C at a temperature of 20-40 ° C / h, a constant temperature of 7- for 15 hours to obtain the mixed melt;
  • the compound containing Cs is Cs 2 CO 3, CsNO 3, CsHCO 3, CsF or CsBF 4;
  • F-containing compound is CsF or CsBF 4;
  • B-containing compound is H 3 BO 3, B 2 O 3 or CsBF 4 ;
  • step b The mixed melt of step b is lowered to a temperature of 400-590 ° C at a temperature of 0.1-5 ° C / h, and the temperature is lowered to 300-440 ° C at a temperature of 0.2-2 ° C / h, and then the temperature is 3-15 ° C. /h cooling rate is reduced to 30 ° C, to obtain CsB 4 O 6 F seed crystal;
  • the crystal is grown in the compound melt by the pulling method: the seed crystal obtained in the step c is fixed on the seed rod, and the seed crystal is lowered from the top of the crystal growth furnace of the melt prepared in the step b to 1 mm above the liquid surface. Preheating for 5 to 60 minutes, then immersing the seed crystals in the liquid surface 1-5 mm, applying a crystal rotation of 2-30 rpm through a crystal growth controller, controlling the temperature to saturate the melt, and raising the seed crystal at a rate of 1-3 mm/day.
  • the seed crystal obtained in step c is fixed on the seed rod, and the seed crystal is lowered from the top of the crystal growth furnace of the melt prepared in step b to 1 mm above the liquid surface. Preheat for 5 to 60 minutes, then let the seed crystals immerse into the liquid surface 1-5mm, and cool at a temperature of 0.1-0.7 °C / h. After 3-10 hours, raise the seed crystal by 1-2mm and continue to the temperature 0.1-0.7. The rate of °C/h is cooled to the end of crystal growth, and the crystal on the seed rod is raised to a temperature of 0.2-2 °C / h to 300-440 ° C, and then reduced to 30 at a rate of 3-15 ° C / h. °C, that is, a CsB 4 O 6 F nonlinear optical crystal is obtained;
  • crystal growth in the compound melt by the ruthenium dropping method first, the seed crystal prepared in the step c is placed on the bottom of the crucible, and then the compound CsB 4 O 6 F polycrystal prepared in the step a is placed in the crucible to seal the platinum crucible. Increase the temperature of the growth furnace to 500-700 ° C, constant temperature for 7-15 hours, adjust the position of the crucible, make the inoculation temperature at 500-625 ° C, and then reduce the crucible at a speed of 1-10 mm / day, while maintaining the growth temperature.
  • the temperature is lowered to 300-440 ° C at a temperature drop rate of 0.2-2 ° C / h, and then lowered to 30 ° C at a rate of 3-15 ° C / h, and the platinum ruthenium is taken out to obtain CsB 4 O. 6 F nonlinear optical crystal.
  • the compound CsB 4 O 6 F polycrystalline powder obtained in step a is uniformly mixed with the flux molar ratio 1:0.1-0.5, and then charged into the washed platinum crucible at a rate of 35-45 ° C / h. heated to 400-700 deg.] C, temperature 7-15 hours, to give a mixed melt;
  • the compound containing Cs is Cs 2 CO 3, CsNO 3, CsHCO 3, CsF or CsBF 4;
  • F-containing compound is CsF or CsBF 4;
  • the B compound is H 3 BO 3 , B 2 O 3 or CsBF 4 ;
  • the flux is CsF, H 3 BO 3 , B 2 O 3 , PbO or PbF 2 ;
  • step b the mixed melt prepared in step b is placed in a single crystal furnace, and then lowered to a temperature of 350-610 ° C at a temperature of 0.1-5 ° C / h, at a rate of 0.2-0.6 ° C / h. Cooling to 300-385 ° C, and then dropping to 30 ° C at a temperature drop rate of 3-10 ° C / h, to obtain a seed crystal of CsB 4 O 6 F;
  • the obtained CsB 4 O 6 F seed crystal is fixed on the seed rod, and the seed crystal is lowered from the top of the crystal growth furnace of the mixed melt prepared in step b to 1 mm above the liquid surface, and preheating 10- 25 minutes, then the seed crystal is brought into contact with the liquid surface, and the temperature is lowered at a temperature of 0.1-2 ° C / h until the end of the crystal growth, the crystal is lifted off the surface of the melt, and then cooled to a temperature of 3-10 ° C / h to 30 At °C, a CsB 4 O 6 F nonlinear optical crystal is obtained.
  • the Cs-containing compound is Cs 2 CO 3 , CsNO 3 , CsHCO 3 , CsF or CsBF 4 ;
  • containing F is compound CsF or CsBF 4 ;
  • B containing compound is H 3 BO 3 , B 2 O 3 or CsBF 4 ;
  • the compound CsB 4 O 6 F polycrystalline powder obtained in the step a is uniformly mixed with the flux molar ratio 1:0.1-1, and then charged into the quartz tube to be heated to 400 at a temperature of 10-50 ° C / h.
  • the compound containing Cs is Cs 2 CO 3, CsNO 3, CsHCO 3, CsF or CsBF 4;
  • F-containing compound is CsF, CsBF 4 or the HF;
  • B-containing compound is H 3 BO 3 , B 2 O 3 or CsBF 4 ;
  • the flux is CsF, H 3 BO 3 , B 2 O 3 , PbO or PbF 2 .
  • step b The compound CsB 4 O 6 F polycrystalline powder obtained in step a is dissolved in 5-30 mL of deionized water, and the incompletely dissolved mixture is ultrasonicated at a temperature of 20-50 ° C for 5-30 minutes to make it sufficient. Mixed to dissolve;
  • step b the mixed solution obtained in step b is transferred to a clean, non-contaminated volume of 100 mL of the high pressure reactor lining, and the reactor is tightly sealed;
  • step b The compound CsB 4 O 6 F polycrystalline powder obtained in step a is placed in a clean glass container, 20-100 mL of deionized water is added, and then ultrasonically treated for 5 to 60 minutes to be thoroughly mixed and dissolved, and then Add HF and CsOH to adjust the pH of the solution 8-11;
  • step c Seal the container containing the solution in step b with a weighing paper, and place it in a static environment without shaking, pollution, and air convection.
  • the sealing hole is controlled to control the evaporation rate to 0.2-2 mL/day. Allow to stand at room temperature for 5-20 days;
  • step c grows crystal particles at the bottom of the container until the crystal particle size no longer changes significantly, and the growth ends to obtain a seed crystal
  • the preparation method of the bismuth fluoroborate nonlinear optical crystal of the present invention, the bismuth fluoroborate polycrystalline powder used in preparing the mixed melt or the mixed solution, may also be replaced by the directly weighed raw material, that is, the compound containing Cs, including
  • CsBF 4 contains F as compound CsF or CsBF 4 ;
  • B-containing compound is H 3 BO 3 , B 2 O 3 or CsBF 4 .
  • the container used in the preparation process is platinum ruthenium, iridium, ceramic enamel, quartz tube, conical flask, beaker, and the inner liner is PTFE lining. Or a stainless steel lined hydrothermal kettle with a platinum sleeve.
  • the container is a quartz tube, a vacuum is required before sealing to avoid the evaporation of the raw material during the reaction to cause the quartz tube to burst.
  • the container is a conical flask or beaker, the container must be cleaned with acid, then rinsed with deionized water and allowed to dry.
  • the electric resistance furnace used in the preparation process is a muffle furnace or a drying oven.
  • the method for preparing a bismuth borofluoride nonlinear optical crystal according to the present invention wherein a CsB 4 O 6 F nonlinear optical crystal having a size of centimeter is obtained by using the method, using a large size crucible or a container, and prolonging the growth period of the crystal,
  • the corresponding large-sized nonlinear optical crystal CsB 4 O 6 F can be obtained.
  • the crystal is easy to grow, transparent and unwrapped, and has a fast growth rate, low cost and easy to obtain large.
  • the advantages of size crystals are.
  • the large-sized CsB 4 O 6 F nonlinear optical crystal obtained is oriented according to the crystallographic data of the crystal, according to the desired angle and thickness. Cutting the crystal with the cross-sectional size and polishing the light-passing surface of the crystal can be used as a nonlinear optical device.
  • the CsB 4 O 6 F nonlinear optical crystal has a wide light transmission band, stable physical and chemical properties, and high mechanical hardness. Fragmentation and deliquescence, easy to cut, polished and preserved.
  • Figure 1 is a powder XRD spectrum of the compound CsB 4 O 6 F of the present invention, and the spectrum is consistent with the theoretical XRD pattern, demonstrating the presence of the compound CsB 4 O 6 F;
  • Figure 2 is a structural view of a CsB 4 O 6 F crystal of the present invention.
  • 3 is a working principle diagram of a nonlinear optical device fabricated by using a CsB 4 O 6 F crystal of the present invention, wherein 1 is a laser, 2 is a light beam, 3 is a CsB 4 O 6 F crystal, 4 is an outgoing beam, and 5 is a filter. .
  • the compound CsB 4 O 6 F was synthesized by solid state reaction according to the reaction formula: CsF+4H 3 BO 3 ⁇ CsB 4 O 6 F+6H 2 O ⁇ :
  • the compound CsB 4 O 6 F was synthesized by solid state reaction according to the reaction formula: 12CsHCO 3 +4CsBF 4 ⁇ CsB 4 O 6 F+15CsF+6H 2 O ⁇ +12CO 2 ::
  • CsHCO 3 and CsBF 4 were uniformly mixed at a molar ratio of 2:3, charged with platinum crucible, placed in a muffle furnace and heated to 450 ° C, and kept at a constant temperature for 56 hours to obtain a compound CsB 4 O 6 F.
  • the compound CsB 4 O 6 F was synthesized by solid state reaction according to the reaction formula: 6Cs 2 CO 3 +4CsBF 4 ⁇ CsB 4 O 6 F+15CsF+6CO 2 ::
  • the Cs 2 CO 3 and CsBF 4 were uniformly mixed at a molar ratio of 2:3, charged with platinum crucible, placed in a muffle furnace and heated to 460 ° C, and kept at a constant temperature for 96 hours to obtain a compound CsB 4 O 6 F.
  • the compound CsB 4 O 6 F was synthesized by solid phase synthesis according to the reaction formula: 12CsNO 3 +4CsBF 4 ⁇ CsB 4 O 6 F+15CsF+6N 2 O 5 :
  • the CsNO 3 and CsBF 4 were uniformly mixed at a molar ratio of 2:3, charged with platinum crucible, placed in a muffle furnace and heated to 470 ° C, and kept at a constant temperature for 96 hours to obtain a compound CsB 4 O 6 F.
  • the compound CsB 4 O 6 F was synthesized by vacuum encapsulation according to the reaction formula: 12CsHCO 3 +4CsBF 4 ⁇ CsB 4 O 6 F+15CsF+6H 2 O ⁇ +12CO 2 ::
  • the compound CsB 4 O 6 F was synthesized by vacuum encapsulation according to the reaction formula: 6Cs 2 CO 3 +4CsBF 4 ⁇ CsB 4 O 6 F+15CsF+6CO 2 ::
  • the compound CsB 4 O 6 F was synthesized by vacuum encapsulation according to the reaction formula: 12CsNO 3 +4CsBF 4 ⁇ CsB 4 O 6 F+15CsF+6N 2 O 5 :
  • the compound CsB 4 O 6 F obtained according to Example 1 and the flux were uniformly mixed with a CsF molar ratio of 1:0.1, and charged into a platinum platinum crucible and placed in a single crystal growth furnace at a rate of 35 ° C / h. Heating to 400 ° C, constant temperature for 7 hours, to obtain a mixed melt;
  • Preparation of seed crystal The prepared mixed melt was placed in a single crystal furnace, cooled to 350 ° C at a rate of 0.1 ° C / h, cooled to 300 ° C at a rate of 0.2 ° C / h, and then at a temperature of 3 ° C / The rate of h is reduced to 30 ° C to obtain a CsB 4 O 6 F seed crystal;
  • Crystal growth The obtained CsB 4 O 6 F seed crystal is fixed on the seed rod, and the seed crystal is lowered from the top of the crystal growth furnace containing the prepared mixed melt to 1 mm above the liquid surface, and preheated for 10 minutes, then The seed crystal is brought into contact with the liquid surface, and the temperature is lowered at a temperature of 0.1 ° C / h until the end of the crystal growth, and the crystal on the seed rod is raised, and then the temperature is lowered to 30 ° C at a temperature of 3 ° C / h, that is, the size is 12 mm ⁇ 13 mm x 16 mm CsB 4 O 6 F nonlinear optical crystal.
  • the compound CsB 4 O 6 F obtained according to Example 2 was mixed with a flux of PbF 2 by a molar ratio of 1:0.5, placed in a single crystal growth furnace, and heated to a temperature of 45 ° C / h to 700 ° C, at a constant temperature of 15 hours. , obtaining a mixed melt;
  • Preparation of seed crystal The prepared mixed melt was placed in a single crystal furnace, cooled to 610 ° C at a temperature of 5 ° C / h, cooled to 385 ° C at a rate of 0.6 ° C / h, and then at a temperature of 10 ° C / The rate of h is lowered to 30 ° C to obtain a seed crystal of CsB 4 O 6 F crystal;
  • Crystal growth The obtained CsB 4 O 6 F seed crystal is fixed on the seed rod, and the seed crystal is lowered from the top of the crystal growth furnace containing the prepared mixed melt to 1 mm above the liquid surface, and preheated for 25 minutes, then The seed crystal is brought into contact with the liquid surface, and the temperature is lowered at a temperature of 2 ° C / h until the end of the crystal growth, and the crystal on the seed rod is raised, and then the temperature is lowered to 30 ° C at a temperature of 10 ° C / h, that is, the size is 15 mm ⁇ 17 mm x 18 mm CsB 4 O 6 F nonlinear optical crystal.
  • the compound CsB 4 O 6 F obtained according to Example 3 was mixed with a flux of B 2 O 3 by a molar ratio of 1:0.5 into a cleaned platinum crucible, and placed in a single crystal growth furnace at a temperature of 40 ° C / h. The rate is raised to 690 ° C, constant temperature for 10 hours to obtain a mixed melt;
  • Preparation of seed crystal The prepared mixed melt was placed in a single crystal furnace, cooled to 580 ° C at a rate of 3 ° C / h, cooled to 330 ° C at a rate of 0.6 ° C / h, and then at a temperature of 8 ° C / The rate of h is lowered to 30 ° C to obtain a seed crystal of CsB 4 O 6 F crystal;
  • Crystal growth The obtained CsB 4 O 6 F seed crystal is fixed on the seed rod, and the seed crystal is lowered from the top of the crystal growth furnace containing the prepared mixed melt to 1 mm above the liquid surface, and preheated for 20 minutes, then The seed crystal is brought into contact with the liquid surface, and the temperature is lowered at a temperature of 0.3 ° C / h until the end of the crystal growth, and the crystal on the seed rod is raised to a temperature of 8 ° C / h to 30 ° C, that is, the size is 12 mm ⁇ 15 mm. ⁇ 19 mm CsB 4 O 6 F nonlinear optical crystal.
  • the compound CsB 4 O 6 F obtained according to Example 4 and the flux were mixed with PbO molar ratio of 1:0.2 and charged with platinum crucible, placed in a single crystal growth furnace, and heated to a temperature of 660 ° C at a rate of 35 ° C / h. Constant temperature for 8 hours to obtain a mixed melt;
  • Preparation of seed crystal The prepared mixed melt was placed in a single crystal furnace, cooled to 575 ° C at a rate of 2 ° C / h, cooled to 380 ° C at a rate of 0.2 ° C / h, and then at a temperature of 7 ° C / The rate of h is reduced to 30 ° C to obtain a CsB 4 O 6 F seed crystal;
  • Crystal growth The obtained CsB 4 O 6 F seed crystal is fixed on the seed rod, and the seed crystal is lowered from the top of the crystal growth furnace containing the prepared mixed melt to 1 mm above the liquid surface, and preheated for 25 minutes, then The seed crystal is brought into contact with the liquid surface, and the temperature is lowered at a temperature of 0.1 ° C / h until the end of the crystal growth, and the crystal on the seed rod is raised to a temperature of 7 ° C / h to 30 ° C, that is, the size is 10 mm ⁇ 12 mm. ⁇ 15 mm CsB 4 O 6 F nonlinear optical crystal.
  • Preparation of seed crystal The prepared mixed melt was placed in a single crystal furnace, cooled to 570 ° C at a rate of 2.4 ° C / h, cooled to 385 ° C at a rate of 0.15 ° C / h, and then at a temperature of 7.5 ° C / The rate of h is reduced to 30 ° C to obtain a CsB 4 O 6 F seed crystal;
  • Crystal growth The obtained CsB 4 O 6 F seed crystal is fixed on the seed rod, and the seed crystal is lowered from the top of the crystal growth furnace containing the prepared mixed melt to 1 mm above the liquid surface, and preheated for 20 minutes, then The seed crystal is brought into contact with the liquid surface, and the temperature is lowered at a temperature of 0.15 ° C / h until the end of the crystal growth, and the crystal on the seed rod is raised, and then the temperature is lowered to 30 ° C at a temperature of 7.5 ° C / h, that is, the size is 13 mm ⁇ 14 mm x 16 mm CsB 4 O 6 F nonlinear optical crystal.
  • the compound CsB 4 O 6 F obtained according to Example 6 was mixed with a flux of B 2 O 3 by a molar ratio of 1:0.1, charged into a quartz tube of ⁇ 40 mm, and the quartz tube was evacuated to a vacuum of 1 ⁇ 10 -3 .
  • the compound CsB 4 O 6 F obtained according to Example 7 was mixed with a fluxing agent in a CsF molar ratio of 1:1, and was placed in a quartz tube of ⁇ 40 mm, and the quartz tube was evacuated to a vacuum of 1 ⁇ 10 -3 Pa.
  • Vacuum-packed with a flame gun placed in a muffle furnace, heated to 700 ° C at a temperature of 50 ° C / h, constant temperature for 96 hours, then cooled to 450 ° C at a rate of 1.5 ° C / day, and then at a temperature of 5 ° C / The rate of h was lowered to 30 ° C, and the quartz tube was cut to obtain a CsB 4 O 6 F nonlinear optical crystal having a size of 15 mm ⁇ 18 mm ⁇ 23 mm.
  • the compound CsB 4 O 6 F obtained according to Example 8 was mixed with a flux of H 3 BO 3 by a molar ratio of 1:0.3, charged into a quartz tube of ⁇ 40 mm, and the quartz tube was evacuated to a vacuum of 1 ⁇ 10 ⁇ 3 Pa, vacuum-packed with a flame gun, placed in a muffle furnace, heated to 500 ° C at a temperature of 35 ° C / h, constant temperature for 50 hours, then cooled to 430 ° C at a rate of 0.5 ° C / day, and then temperature The rate of 4 ° C / h was lowered to 30 ° C, and the quartz tube was cut to obtain a CsB 4 O 6 F nonlinear optical crystal having a size of 14 mm ⁇ 16 mm ⁇ 17 mm.
  • the compound CsB 4 O 6 F obtained according to Example 9 and the flux were mixed with PbO molar ratio of 1:0.4, charged into a quartz tube of ⁇ 40 mm, and the quartz tube was evacuated to a vacuum of 1 ⁇ 10 -3 Pa.
  • the vacuum is 1 ⁇ 10 -3 Pa, vacuum-packed with a flame gun, placed in a muffle furnace, heated to 510 ° C at a temperature of 37 ° C / h, constant temperature for 96 hours, and then at a rate of 1.2 ° C / day
  • the temperature was lowered to 445 ° C, and then lowered to 30 ° C at a rate of 3.5 ° C / h, and the quartz tube was cut to obtain a CsB 4 O 6 F nonlinear optical crystal having a size of 14 mm ⁇ 16 mm ⁇ 17 mm.
  • the compound CsB 4 O 6 F obtained according to Example 10 was placed in a cleaned platinum crucible, placed in a muffle furnace, and heated to a temperature of 40 ° C / h to 700 ° C, and kept at a constant temperature for 15 hours to obtain a mixed melt;
  • the obtained mixed melt was cooled to 590 ° C at a temperature of 5 ° C / h, cooled to 440 ° C at a rate of 2 ° C / h, and then lowered to 30 ° C at a rate of 15 ° C / h to obtain CsB 4 O 6 F seed crystal;
  • the obtained CsB 4 O 6 F seed crystal was fixed on the seed rod, and the seed crystal was dropped from the top of the crystal growth furnace equipped with the prepared mixed melt to 1 mm above the liquid surface, preheated for 5 minutes, and then the seed crystal was obtained. 5mm into the liquid surface, 30rpm crystallization was applied by crystal growth controller, the temperature was controlled to saturate the melt, the seed crystal was lifted at a speed of 3mm/day, and the crystal was finished at the end of the crystal growth.
  • the crystal on the seed rod was raised to the temperature 2
  • the rate of °C/h was lowered to 440 ° C, and then dropped to 30 ° C at a rate of 15 ° C / h, that is, a CsB 4 O 6 F nonlinear optical crystal having a size of 12 mm ⁇ 15 mm ⁇ 16 mm was obtained.
  • Example 2 The compound CsB 4 O 6 F obtained in Example 2 was charged with platinum rhodium, placed in a single crystal growth furnace, and heated to 400 ° C at a temperature of 20 ° C / h, and kept at a constant temperature for 7 hours to obtain a mixed melt;
  • the obtained mixed melt was cooled to 400 ° C at a rate of 0.1 ° C / h, cooled to 300 ° C at a rate of 0.2 ° C / h, and then lowered to 30 ° C at a rate of 3 ° C / h to obtain CsB 4 O 6 F seed crystal;
  • the obtained CsB 4 O 6 F seed crystal was fixed on the seed rod, and the seed crystal was dropped from the top of the crystal growth furnace containing the prepared melt to 1 mm above the liquid surface, preheated for 5 minutes, and then the seed crystal was submerged.
  • the liquid level is 1 mm
  • a crystal rotation of 2 rpm is applied by a crystal growth controller, the temperature is controlled to saturate the melt, the seed crystal is lifted at a speed of 1 mm/day, and the crystal growth is completed until the end of the crystal growth, and the crystal on the seed crystal rod is raised at a temperature of 0.2 ° C.
  • the rate of /h was lowered to 300 ° C, and then dropped to 30 ° C at a rate of 3 ° C / h, that is, a CsB 4 O 6 F nonlinear optical crystal having a size of 11 mm ⁇ 14 mm ⁇ 15 mm was obtained.
  • the obtained mixed melt was cooled to 580 ° C at a temperature of 4 ° C / h, cooled to 440 ° C at a temperature of 1 ° C / h, and then lowered to 30 ° C at a rate of 6 ° C / h to obtain CsB 4 O 6 F seed crystal;
  • the obtained CsB 4 O 6 F seed crystal was fixed on the seed rod, and the seed crystal was dropped from the top of the crystal growth furnace containing the prepared melt to 1 mm above the liquid surface, preheated for 15 minutes, and then the seed crystal was submerged.
  • the liquid level is 3 mm, and a crystal rotation of 8 rpm is applied by a crystal growth controller, the temperature is controlled to saturate the melt, the seed crystal is lifted at a speed of 3 mm/day, and the crystal growth is completed until the end of the crystal growth, and the crystal on the seed crystal rod is raised at a temperature of 1 ° C.
  • the rate of /h was lowered to 440 ° C, and then dropped to 30 ° C at a rate of 6 ° C / h, that is, a CsB 4 O 6 F nonlinear optical crystal having a size of 17 mm ⁇ 19 mm ⁇ 20 mm was obtained.
  • Example 4 The compound CsB 4 O 6 F obtained in Example 4 was charged with platinum rhodium, placed in a single crystal growth furnace, and heated to a temperature of 20 ° C / h to 700 ° C, and kept at a constant temperature for 15 hours to obtain a mixed melt;
  • the obtained mixed melt was cooled to 590 ° C at a temperature of 5 ° C / h, cooled to 440 ° C at a rate of 2 ° C / h, and then lowered to 30 ° C at a rate of 15 ° C / h, and platinum ruthenium was taken out.
  • CsB 4 O 6 F seed crystal
  • the obtained seed crystal was placed on the bottom of the platinum crucible, and then the obtained compound CsB 4 O 6 F was placed in a platinum crucible, and the platinum crucible was sealed and placed in a crucible lowering furnace, and the temperature was raised to 700 ° C, and the temperature was maintained for 15 hours.
  • Example 5 The compound CsB 4 O 6 F obtained in Example 5 was charged with platinum ruthenium, placed in a single crystal growth furnace, and heated to 675 ° C at a temperature of 40 ° C / h, and kept at a constant temperature for 7 hours to obtain a mixed melt;
  • the obtained mixed melt was cooled to 575 ° C at a rate of 0.1 ° C / h, cooled to 380 ° C at a rate of 1.5 ° C / h, and then lowered to 30 ° C at a rate of 12 ° C / h, and platinum ruthenium was taken out.
  • the obtained seed crystal was placed at the bottom of the platinum crucible, and then the obtained compound CsB 4 O 6 F was placed in a platinum crucible, and the platinum crucible was sealed and placed in a crucible lowering furnace, and the temperature was raised to 500 ° C, and the temperature was maintained for 7 hours.
  • the obtained mixed melt was cooled to 570 ° C at a temperature of 3 ° C / h, cooled to 350 ° C at a temperature of 1 ° C / h, and then lowered to 30 ° C at a rate of 15 ° C / h, and platinum iridium was taken out.
  • the obtained seed crystal was placed on the bottom of the platinum crucible, and the obtained compound CsB 4 O 6 F was placed in a platinum crucible, and the platinum crucible was sealed and placed in a crucible lowering furnace, and the temperature was raised to 680 ° C for 12 hours.
  • Example 2 The compound CsB 4 O 6 F obtained in Example 2 was charged with platinum rhodium, placed in a single crystal growth furnace, and heated to 630 ° C at a temperature of 40 ° C / h, and kept at a constant temperature for 18 hours to obtain a mixed melt;
  • the obtained mixed melt was cooled to 565 ° C at a temperature of 5 ° C / h, cooled to 380 ° C at a rate of 2 ° C / h, and then lowered to 30 ° C at a rate of 8 ° C / h to obtain CsB 4 O 6 F seed crystal;
  • the obtained CsB 4 O 6 F seed crystal was fixed on the seed rod, and the seed crystal was dropped from the top of the crystal growth furnace containing the prepared melt to 1 mm above the liquid surface, preheated for 60 minutes, and then the seed crystal was immersed.
  • the liquid surface is 5mm, and the temperature is lowered at a temperature of 0.7 °C / h.
  • the seed crystal is lifted by 2 mm, and the temperature is further lowered at a temperature of 0.7 ° C / h until the end of crystal growth, and the crystal on the seed rod is raised to a temperature of 2
  • the rate of °C/h was lowered to 440 ° C, and then dropped to 30 ° C at a rate of 15 ° C / h, that is, a CsB 4 O 6 F nonlinear optical crystal having a size of 4 mm ⁇ 6 mm ⁇ 9 mm was obtained.
  • the compound CsB 4 O 6 F obtained according to Example 3 was charged into platinum crucible, placed in a single crystal growth furnace, and heated to 640 ° C at a temperature of 20 ° C / h, and kept at a constant temperature for 24 hours to obtain a mixed melt;
  • the obtained mixed melt was cooled to 560 ° C at a rate of 6 ° C / h, cooled to 390 ° C at a rate of 1.8 ° C / h, and then lowered to 30 ° C at a rate of 3.5 ° C / h to obtain CsB 4 O. 6 F seed crystal;
  • Crystal growth in the compound melt by a bubble method the obtained CsB 4 O 6 F seed crystal is fixed on the seed rod, and the seed crystal is lowered from the top of the crystal growth furnace containing the prepared melt to above the liquid surface 1mm, preheat for 5 minutes, then immerse the seed crystal 1mm, and cool at a temperature of 0.1 °C / h. After 10 hours, raise the seed crystal by 1mm and continue to cool at a rate of 0.1 °C / h until the end of crystal growth.
  • the crystal on the seed rod is raised to a temperature of 0.2 ° C / h to 300 ° C, and then reduced to 30 ° C at a rate of 3 ° C / h, that is, a size of 13 mm ⁇ 18 mm ⁇ 24 mm CsB 4 O 6 F nonlinear optical crystal.
  • the compound CsB 4 O 6 F obtained according to Example 1 was placed in a cleaned glass container, 100 mL of deionized water was added, and then ultrasonically treated for 5 minutes to be thoroughly mixed and dissolved, and then HF and CsOH were added to adjust the pH of the solution to 8 ;
  • the container containing the solution is sealed with a weighing paper, placed in a static environment without shaking, no pollution, no air convection, and the sealing hole is controlled to control the evaporation rate to 2 mL/day, and allowed to stand for 5 days;
  • the remaining solution is filtered with a qualitative filter paper to filter the other impurities in the crystal grains and the solution, and the seed crystal with better quality is selected, the seed crystal is fixed with platinum wire, suspended in the filtered solution, and the evaporation rate of the sealing hole is closed.
  • the control was 2 mL/day, and it was allowed to stand at room temperature for 30 days to obtain a CsB 4 O 6 F nonlinear optical crystal having a size of 8 mm ⁇ 14 mm ⁇ 17 mm.
  • the container containing the solution is sealed with a weighing paper, placed in a static environment without shaking, no pollution, no air convection, and the sealing hole is controlled to control the evaporation rate to 0.2 mL/day, and allowed to stand for 20 days;
  • the remaining solution was filtered with a qualitative filter paper to remove other impurities in the crystal grains and the solution, and the seed crystal was fixed with platinum wire, suspended in the filtered solution, and the evaporation rate was controlled to 0.2 mL/day in the sealing hole. After standing at room temperature for 30 days, a CsB 4 O 6 F nonlinear optical crystal having a size of 4 mm ⁇ 8 mm ⁇ 9 mm was obtained.
  • the compound CsB 4 O 6 F obtained according to Example 1 was placed in 5 mL of deionized water, and the incompletely dissolved mixture was treated in ultrasonic waves at a temperature of 20 ° C for 5 minutes to be thoroughly mixed;
  • the high pressure reaction kettle was placed in an incubator, heated to 350 ° C at a temperature of 50 ° C / h, constant temperature for 3 days, and then cooled to room temperature at a temperature drop rate of 5 ° C / day, the high pressure reactor was opened, and the size was obtained. 8 mm ⁇ 9 mm ⁇ 15 mm CsB 4 O 6 F nonlinear optical crystal.
  • the high pressure reaction kettle was placed in an incubator, heated to a temperature of 5 ° C / h to 150 ° C, constant temperature for 15 days, and then cooled to room temperature at a temperature drop rate of 30 ° C / day, open the high pressure reactor, the size is obtained 22 mm ⁇ 24 mm ⁇ 27 mm CsB 4 O 6 F nonlinear optical crystal.
  • the compound CsB 4 O 6 F obtained according to Example 2 was placed in 8 mL of deionized water, and the incompletely dissolved mixture was treated in ultrasonic waves at a temperature of 45 ° C for 30 minutes to be thoroughly mixed;
  • the mixture was transferred to a clean, non-contaminating inner liner of a 100 mL volumetric autoclave, and the reactor was tightly sealed;
  • the high pressure reaction kettle was placed in an incubator, heated to 330 ° C at a temperature of 40 ° C / h, constant temperature for 10 days, and then cooled to room temperature at a temperature drop rate of 8 ° C / day, and the high pressure reactor was opened, and the size was obtained. 12 mm x 18 mm x 20 mm CsB 4 O 6 F nonlinear optical crystal.
  • the arbitrary CsB 4 O 6 F crystals obtained in Examples 1-33 were processed in the matching direction, placed at the position of 3 as shown in Fig. 3, and the Q-Nd:YAG laser was used as the light source at room temperature.
  • the Q-Nd:YAG laser was used as the light source at room temperature.
  • an infrared beam 2 having a wavelength of 1064 nm emitted from a Q-switched N-type YAG laser 1 is incident on a CsB 4 O 6 F single crystal 3, and a green octave light having a wavelength of 532 nm is generated, and the output intensity is about KDP of the same condition. 2 times.
  • the arbitrary CsB 4 O 6 F crystals obtained in Examples 1-33 were processed in the matching direction, and placed at the position of 3 as shown in Fig. 3.
  • a Q-switched Nd:YAG laser was used as the light source, and the incident wavelength was used.
  • an infrared beam 2 emitting a wavelength of 532 nm from a Q-switched Nd:YAG laser 1 is incident on a CsB 4 O 6 F single crystal 3, producing a frequency doubled light having a wavelength of 266 nm, and the output intensity is about 0.5 times that of the equivalent condition BBO. .
  • the arbitrary CsB 4 O 6 F crystals obtained in Examples 1-33 were processed in the matching direction, placed at the position of 3 as shown in Fig. 3, and the Q-Nd:YAG laser was used as the light source at room temperature.
  • the Q-Nd:YAG laser was used as the light source at room temperature.
  • an infrared beam 2 having a wavelength of 355 nm emitted from a Q-switched-Nd:YAG laser 1 is incident on a CsB 4 O 6 F single crystal 3, and a deep ultraviolet double-frequency light output having a wavelength of 177.3 nm can be observed.

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Abstract

化合物氟硼酸铯和氟硼酸铯非线性光学晶体及制备方法和用途，所述化合物的化学式为CsB 4O 6F，分子量为291.15，为晶体结构，采用固相合成法或真空封装法制成，该晶体的化学式为CsB 4O 6F，分子量为291.15，属于正交晶系，空间群为Pna2 1，晶胞参数为 a=７．９２４１Å，ｂ＝１１．３９９６Å，ｃ＝６．６６３８Å，α＝β＝γ＝90°，单胞体积为６０１．９５Å３。该晶体的倍频效应约为 KH 2PO 4(KDP)的2倍，紫外吸收边短于190nm。CsB 4O 6F采用熔体法，高温熔液法，真空封装法，水热法或室温溶液法生长晶体，该晶体在空气中不潮解，化学稳定性好，可作为紫外、深紫外非线性光学晶体在全固态激光器中获得应用。

Description

化合物氟硼酸铯和氟硼酸铯非线性光学晶体及制备方法和用途 技术领域
本发明涉及一种化合物氟硼酸铯CsB4O6F和氟硼酸铯CsB4O6F非线性光学晶体及制备方法和用途。
背景技术
非线性光学晶体作为全固态激光器的重要部件，其研究一直受到国内外学者广泛关注，经过半个世纪的研究，已发现一系列性能优异的非线性光学晶体。可见光波段的代表性的非线性光学晶体有KTiOPO4(KTP)，KH2PO4(KDP)等。在紫外波段，已经产业化的非线性光学晶体LiB3O5(LBO)、CsB3O5(CBO)、CsLiB6O10(CLBO)和BaB2O4(BBO)等。但是在200nm以下的深紫外波段，实用化的非线性光学晶体只有KBe2BO3F2(KBBF)。由于该晶体生长周期长、含有剧毒Be元素、层状生长习性等，一定程度上限制了其应用。因此，探索具有更加优良性能的新型深紫外非线性光学晶体是十分有必要的。
本发明在此前的研究中，发明了化合物氟硼酸铵NH4B4O6F和氟硼酸铵NH4B4O6F非线性光学晶体，专利申请号201611128283.3，本发明与氟硼酸铵NH4B4O6F的主要区别在于，NH4B4O6F中NH4 +与阴离子基团以氢键连接，而CsB4O6F中Cs+与阴离子基团以离子键连接，从而导致两者结构，生长习性完全不同，且生长工艺关键参数，晶体性能等均与NH4B4O6F不同。
发明内容
本发明目的在于，提供一种化合物氟硼酸铯，该化合物的化学式为CsB4O6F，分子量为291.15，采用固相反应法或真空封装法制备。
本发明的另一个目的在于，提供氟硼酸铯CsB4O6F非线性光学晶体，该晶体的化学式为CsB4O6F，分子量为291.15，晶体属正交晶系，空间群Pna21，晶胞参数为
Figure PCTCN2017092331-appb-000001
Figure PCTCN2017092331-appb-000002
α＝β＝γ＝90°，单胞体积为
Figure PCTCN2017092331-appb-000003
本发明再一个目的在于，提供氟硼酸铯CsB4O6F非线性光学晶体的制备方法，采用熔体法，高温熔液法，真空封装法，水热法或室温溶液法生长晶体。
本发明又一个目的在于，提供氟硼酸铯CsB4O6F非线性光学晶体的用途。
本发明所述的一种化合物氟硼酸铯，该化合物的化学式为CsB4O6F，分子量为291.15，该化合物为晶体结构。
所述化合物氟硼酸铯的制备方法，采用固相合成法或真空封装法制备化合物，具体操作按下列步骤进行：
所述固相合成法制备化合物氟硼酸铯：
将含Cs化合物、含B化合物和含F化合物按摩尔比Cs∶B∶F＝0.5-2∶3-5∶0.5-2混合均匀，装入铂金坩埚中，然后放入马弗炉，升温至350-600℃，恒温3-96小时，即得到化合物CsB4O6F；所述含Cs化合物为Cs2CO3、CsNO3、CsHCO3、CsF或CsBF4；含F为化合物CsF或CsBF4；含B化合物为H3BO3、B2O3或CsBF4。
所述真空封装法制备化合物氟硼酸铯：
将含Cs化合物、含B化合物和含F化合物按摩尔比Cs∶B∶F＝0.5-2∶3-5∶0.5-2混合均匀，装入Φ40mm的石英管中，将石英管抽真空，真空度达到1×10-3Pa，高温密封，放入马弗炉中，以10-50℃的速率升温至350-600℃，恒温3-96小时，即得到化合物CsB4O6F。所述含Cs化合物为Cs2CO3、CsNO3、CsHCO3、CsF或CsBF4；含F为化合物CsF或CsBF4；含B化合物为H3BO3、B2O3或CsBF4。
一种氟硼酸铯非线性光学晶体，该晶体的化学式为CsB4O6F，分子量为291.15，晶体属正交晶系，空间群为Pna21，晶胞参数为
Figure PCTCN2017092331-appb-000004
α＝β＝γ＝90°，单胞体积为
Figure PCTCN2017092331-appb-000005
所述氟硼酸铯非线性光学晶体的制备方法，采用熔体法，高温熔液法，真空封装法，水热法或室温溶液法生长晶体；
所述熔体法生长氟硼酸铯非线性光学晶体的具体操作按下列步骤进行：
a、将含Cs化合物、含B化合物和含F化合物按摩尔比Cs∶B∶F＝0.5-2∶3-5∶0.5-2混合均匀，装入铂金坩埚，然后放入马弗炉，升温至350-600℃，恒温3-96小时，即得到化合物CsB4O6F多晶粉末，所述含Cs化合物为Cs2CO3、CsNO3、CsHCO3、CsF或CsBF4；含F为化合物CsF或CsBF4；含B化合物为H3BO3、B2O3或CsBF4；
b、将得到的化合物CsB4O6F多晶粉末装入洗净的铂金坩埚中，放入马弗炉中，以温度20-40℃/h的速率升温至400-700℃，恒温7-15小时，得到混合熔体；所述含Cs化合物为Cs2CO3、CsNO3、CsHCO3、CsF或CsBF4；含F为化合物CsF或CsBF4；含B化合物为H3BO3、B2O3或CsBF4；
c、将步骤b的混合熔体以温度0.1-5℃/h降温速率降至400-590℃，以温度0.2-2℃/h的速率降温至300-440℃，再以温度3-15℃/h降温速率降至30℃，得到CsB4O6F籽晶；
d、采用提拉法在化合物熔体中生长晶体：将步骤c得到的籽晶固定于籽晶杆上，从步骤b制得的熔体的晶体生长炉顶部将籽晶下降至液面上方1mm，预热5-60分钟，然后使籽晶没入液面1-5mm，通过晶体生长控制仪施加2-30rpm的晶转，控制温度使熔体饱和，以1-3mm/天的速度提升籽晶，恒温至晶体生长结束，提出籽晶杆上的晶体，以温度0.2-2℃/h的速率降温至300-440℃，再以温度3-15℃/h的速率降至30℃，即得到CsB4O6F非线性光学晶体；
或用泡生法在化合物熔体中生长晶体：将步骤c得到的籽晶固定于籽晶杆上，从步骤b制得的熔体的晶体生长炉顶部将籽晶下降至液面上方1mm，预热5-60分钟，然后使籽晶没入液面1-5mm，以温度0.1-0.7℃/h的速率降温，3-10小时后，将籽晶提升1-2mm，继续以温度0.1-0.7℃/h的速率降温至晶体生长结束，提出籽晶杆上的晶体，以温度0.2-2℃/h的速率降温至300-440℃，再以温度3-15℃/h的速率降至30℃，即得到CsB4O6F非线性光学晶体；
或用坩埚下降法在化合物熔体中生长晶体：先将步骤c制备的籽晶放在坩埚底部，然后 再将步骤a制备的化合物CsB4O6F多晶放入坩埚中，将铂金坩埚密封，将生长炉温度升高至500-700℃，恒温7-15小时，调整坩埚位置，使接种温度在500-625℃，再以1-10mm/天的速度降低坩埚，同时，保持生长温度不变，待生长结束后，以温度0.2-2℃/h的降温速率降至300-440℃，再以温度3-15℃/h的速率降至30℃，取出铂金坩埚，即得到CsB4O6F非线性光学晶体。
所述高温熔液法生长氟硼酸铯非线性光学晶体的具体操作按下列步骤进行：
a、将含Cs化合物、含B化合物和含F化合物按摩尔比Cs∶B∶F＝0.5-2∶3-5∶0.5-2混合均匀，装入铂金坩埚，然后放入马弗炉，升温至350-600℃，恒温3-96小时，即得到化合物CsB4O6F多晶粉末，所述含Cs化合物为Cs2CO3、CsNO3、CsHCO3、CsF或CsBF4；含F为化合物CsF或CsBF4；含B化合物为H3BO3、B2O3或CsBF4；
b、将步骤a得到的化合物CsB4O6F多晶粉末与助熔剂按摩尔比1∶0.1-0.5混合均匀，再装入洗净的铂金坩埚中，以温度35-45℃/h的速率升温至400-700℃，恒温7-15小时，得到混合熔液；所述含Cs化合物为Cs2CO3、CsNO3、CsHCO3、CsF或CsBF4；含F为化合物CsF或CsBF4；含B化合物为H3BO3、B2O3或CsBF4；所述助熔剂为CsF，H3BO3，B2O3，PbO或PbF2；
c、制备籽晶：将步骤b制得的混合熔液置于单晶炉中，然后以温度0.1-5℃/h降温速率降至350-610℃，以温度0.2-0.6℃/h的速率降温至300-385℃，再以温度3-10℃/h的降温速率降至30℃，得到CsB4O6F的籽晶；
d、生长晶体：将得到的CsB4O6F籽晶固定于籽晶杆上，从步骤b制得的混合熔液的晶体生长炉顶部将籽晶下降至液面上方1mm，预热10-25分钟，然后使籽晶与液面接触，以温度0.1-2℃/h的速率降温至晶体生长结束，将晶体提离熔液表面，然后以温度3-10℃/h的速率降温至30℃，即得到CsB4O6F非线性光学晶体。
所述真空封装法生长氟硼酸铯非线性光学晶体的具体操作按下列步骤进行：
a、将含Cs化合物、含B化合物和含F化合物按摩尔比Cs∶B∶F＝0.5-2∶3-5∶0.5-2混合均匀，装入铂金坩埚中，然后放入马弗炉，以温度10-50℃的速率升至温度350-600℃，恒温3-96小时，得到化合物CsB4O6F多晶粉末，所述含Cs化合物为Cs2CO3、CsNO3、CsHCO3、CsF或CsBF4；含F为化合物CsF或CsBF4；含B化合物为H3BO3、B2O3或CsBF4；
b、将步骤a得到的化合物CsB4O6F多晶粉末与助熔剂按摩尔比1∶0.1-1混合均匀，再装入石英管中，以温度10-50℃/h的速率升温至400-700℃，恒温3-96小时，然后以温度0.5-1.5℃/天的速率降温至330-450℃，再以温度2-5℃/h的速率降至30℃，切开石英管，即得到CsB4O6F非线性光学晶体，所述含Cs化合物为Cs2CO3、CsNO3、CsHCO3、CsF或CsBF4；含F为化合物CsF、CsBF4或HF；含B化合物为H3BO3、B2O3或CsBF4；所述助熔剂为CsF，H3BO3，B2O3，PbO或PbF2。
所述水热法生长氟硼酸铯非线性光学晶体的具体操作按下列步骤进行：
a、将含Cs化合物、含B化合物和含F化合物按摩尔比Cs∶B∶F＝0.5-2∶3-5∶0.5-2混合均匀，装入铂金坩埚中，然后放入马弗炉，升至温度350-600℃，恒温3-96小时，得到产物CsB4O6F多晶粉末，所述含Cs化合物Cs2CO3、CsNO3、CsHCO3、CsF或CH3COOCs；含F化合物CsF或HF；含B化合物H3BO3和B2O3；
b、将步骤a得到的化合物CsB4O6F多晶粉末，置入5-30mL去离子水中溶解，将不完全溶解的混合物在温度20-50℃下的超声波处理5-30分钟使其充分混合溶解；
c、将步骤b得到的混合溶液转入到干净、无污染的体积为100mL的高压反应釜的内衬中，并将反应釜旋紧密封；
d、将高压反应釜放置在恒温箱内，以温度5-50℃/h的速率升温至150-350℃，恒温3-15天，再以温度5-30℃/天的降温速率降至室温，即得到CsB4O6F非线性光学晶体。
所述室温溶液法生长氟硼酸铯非线性光学晶体的具体操作按下列步骤进行：
a、将含Cs化合物、含B化合物和含F化合物按摩尔比Cs∶B∶F＝0.5-2∶3-5∶0.5-2混合均匀，装入铂金坩埚中，然后放入马弗炉，升至温度350-600℃，恒温3-96小时，得到产物CsB4O6F多晶粉末，所述含Cs化合物Cs2CO3、CsNO3、CsHCO3、CsF或CH3COOCs；含F化合物CsF或HF；含B化合物H3BO3和B2O3；
b、将步骤a得到的化合物CsB4O6F多晶粉末，放入洗干净的玻璃容器中，加入20-100mL的去离子水，然后超声波处理5-60分钟，使其充分混合溶解，然后加入HF和CsOH调节溶液pH值8-11；
c、将步骤b中装有溶液的容器用称量纸封口，放在无晃动、无污染、无空气对流的静态环境中，将封口扎小孔将蒸发速率控制为0.2-2mL/天，在室温下静置5-20天；
d、待步骤c中的溶液在容器底部长出晶体颗粒，直至晶体颗粒大小不再明显变化，生长结束，得到籽晶；
e、将剩余溶液用定性滤纸将晶粒及溶液中的其它杂质过滤，选择质量较好的籽晶，用铂金丝固定籽晶，将其悬挂于过滤后的溶液中，将封口扎小孔将蒸发速率控制为0.2-2mL/天，在室温下静置生长10-30天，即可得到CsB4O6F非线性光学晶体。
所述氟硼酸铯非线性光学晶体在制备Nd:YAG激光器所输出的1064nm的基频光进行2倍频、3倍频、4倍频、5倍频或6倍频的谐波光输出的用途。
所述氟硼酸铯非线性光学晶体在制备产生低于200nm的深紫外倍频光输出中的用途。
所述化合物氟硼酸铯非线性光学晶体在制备倍频发生器、上或下频率转换器或光参量振荡器中的用途。
本发明所述氟硼酸铯非线性光学晶体的制备方法，在制备混合熔体或混合溶液中所使用的氟硼酸铯多晶粉末，也可以用直接称取的原料代替，即将含Cs化合物、含B化合物和含F化合物按摩尔比Cs∶B∶F＝0.5-2∶3-5∶0.5-2称取并混合均匀，所述含Cs化合物为Cs2CO3、CsNO3、CsHCO3、CsF或CsBF4；含F为化合物CsF或CsBF4；含B化合物为H3BO3、B2O3 或CsBF4。
本发明所述氟硼酸铯非线性光学晶体的制备方法，在制备过程中所用的容器为铂金坩埚，铱坩埚，陶瓷坩埚，石英管，锥形瓶，烧杯，内衬为聚四氟乙烯内衬或装有铂金套管的不锈钢内衬的水热釜。当容器为石英管时，密封之前需要抽真空，避免反应过程中原料挥发使石英管炸裂。当容器为锥形瓶或烧杯，须先用酸将容器清洗干净，再用去离子水润洗，晾干。
本发明所述氟硼酸铯非线性光学晶体的制备方法，在制备过程中所用的电阻炉为马弗炉或干燥箱。
采用本发明所述的氟硼酸铯非线性光学晶体的制备方法，通过该方法获得尺寸为厘米级的CsB4O6F非线性光学晶体，使用大尺寸坩埚或容器，并延长晶体的生长周期，则可获得相应大尺寸的非线性光学晶体CsB4O6F，在该CsB4O6F非线性光学晶体的生长中晶体易长大透明无包裹，具有生长速度快，成本低，容易获得大尺寸晶体等优点。
采用本发明所述的氟硼酸铯非线性光学晶体的制备方法，获得的大尺寸CsB4O6F非线性光学晶体，根据晶体的结晶学数据，将晶体毛胚定向，按所需角度、厚度和截面尺寸切割晶体，将晶体的通光面抛光，即可作为非线性光学器件使用，该CsB4O6F非线性光学晶体具有较宽的透光波段，物化性能稳定，机械硬度大，不易碎裂和潮解，易于切割、抛光加工和保存等优点。
附图说明
图1为本发明化合物CsB4O6F的粉末XRD谱图，谱图与理论XRD图谱一致，证明了化合物CsB4O6F的存在；
图2为本发明CsB4O6F晶体的结构图；
图3为本发明CsB4O6F晶体制作的非线性光学器件的工作原理图，其中1为激光器，2为发出光束，3为CsB4O6F晶体，4为出射光束，5为滤波片。
具体实施方式
以下结合实施例对本发明做进一步描述，需要说明的是，本发明不仅限于所例举出的实施例，任何在本发明基础上做出的改进都不违背本发明精神，本发明所用原料或设备，如无特殊说明，均是商业上可以购买得到的。
实施例1
制备化合物：
按反应式：CsF+2B2O3→CsB4O6F，采用固相合成法合成化合物CsB4O6F：
将CsF，B2O3按摩尔比1:3混合均匀，将CsF，H3BO3按摩尔比2:5混合均匀，装入干净、无污染的体积为28mL的铂金坩埚中，升温至350℃，恒温96小时，即得到化合物CsB4O6F。
实施例2
制备化合物：
按反应式：CsF+4H3BO3→CsB4O6F+6H2O↑，采用固相反应法合成化合物CsB4O6F：
将CsF，H3BO3按摩尔比2:5混合均匀，装入干净、无污染的体积为28mL的铂金坩埚中，升温至600℃，恒温3小时，即得到化合物CsB4O6F。
实施例3
制备化合物：
按反应式：12CsHCO3+4CsBF4→CsB4O6F+15CsF+6H2O↑+12CO2↑，采用固相反应法合成化合物CsB4O6F：
将CsHCO3，CsBF4按摩尔比2:3混合均匀，装入铂金坩埚，置于马弗炉中升温至450℃，恒温56小时，即得到化合物CsB4O6F。
实施例4
制备化合物：
按反应式：6Cs2CO3+4CsBF4→CsB4O6F+15CsF+6CO2↑，采用固相反应法合成化合物CsB4O6F：
将Cs2CO3，CsBF4按摩尔比2:3混合均匀，装入铂金坩埚，置于马弗炉中升温至460℃，恒温96小时，即得到化合物CsB4O6F。
实施例5
制备化合物：
按反应式：12CsNO3+4CsBF4→CsB4O6F+15CsF+6N2O5，采用固相合成法合成化合物CsB4O6F：
将CsNO3，CsBF4按摩尔比2:3混合均匀，装入铂金坩埚，置于马弗炉中升温至470℃，恒温96小时，即得到化合物CsB4O6F。
实施例6
制备化合物：
按反应式：CsF+2B2O3→CsB4O6F，采用真空封装法合成化合物CsB4O6F：
将CsF，B2O3按摩尔比1:3混合均匀，装入Φ40mm的石英管中，将石英管抽真空，真空度达到1×10-3Pa，用火焰枪真空封装，放入马弗炉中，以50℃的速率升温至350℃，恒温96小时，温度降至室温后打开石英管，即得到化合物CsB4O6F。
实施例7
制备化合物：
按反应式：CsF+4H3BO3→CsB4O6F+6H2O↑，采用真空封装法合成化合物CsB4O6F：
将CsF，B2O3按摩尔比2:5混合均匀，装入Φ40mm的石英管中，将石英管抽真空，真空度达到1×10-3Pa，用火焰枪真空封装，放入马弗炉中，以10℃的速率升温至600℃，恒温96小时，温度降至室温后打开石英管，即得到化合物CsB4O6F。
实施例8
制备化合物：
按反应式：12CsHCO3+4CsBF4→CsB4O6F+15CsF+6H2O↑+12CO2↑，采用真空封装 法合成化合物CsB4O6F：
将CsHCO3，CsBF4按摩尔比2:3混合均匀，装入Φ40mm的石英管中，将石英管抽真空，真空度达到1×10-3Pa，高温密封后置于马弗炉中，以6℃/h的速率升温至470℃，恒温72小时，即得到化合物CsB4O6F。
实施例9
制备化合物：
按反应式：6Cs2CO3+4CsBF4→CsB4O6F+15CsF+6CO2↑，采用真空封装法合成化合物CsB4O6F：
将Cs2CO3，CsBF4按摩尔比2:3混合均匀，装入Φ40mm的石英管中，将石英管抽真空，真空度达到1×10-3Pa，高温密封后置于马弗炉中，以5℃/h的速率升温至460℃，恒温72小时，即得到化合物CsB4O6F。
实施例10
制备化合物：
按反应式：12CsNO3+4CsBF4→CsB4O6F+15CsF+6N2O5，采用真空封装法合成化合物CsB4O6F：
将CsNO3，CsBF4按摩尔比2:3混合均匀，装入Φ40mm的石英管中，将石英管抽真空，真空度达到1×10-3Pa，高温密封后置于马弗炉中，以4℃/h的速率升温至450℃，恒温72小时，即得到化合物CsB4O6F。
实施例11
高温熔液法合成CsB4O6F非线性光学晶体：
依据实施例1得到的化合物CsB4O6F与助熔剂为CsF按摩尔比1∶0.1混合均匀，装入洗净的铂金坩埚，放入单晶生长炉中，以温度35℃/h的速率升温至400℃，恒温7小时，得到混合熔液；
制备籽晶：将制得的混合熔液置于单晶炉中，以温度0.1℃/h的速率降温至350℃，以温度0.2℃/h的速率降温至300℃，再以温度3℃/h的速率降至30℃，得到CsB4O6F籽晶；
生长晶体：将得到的CsB4O6F籽晶固定于籽晶杆上，从装有制得的混合熔液的晶体生长炉顶部将籽晶下降至液面上方1mm，预热10分钟，然后使籽晶与液面接触，以温度0.1℃/h的速率降温至晶体生长结束，提出籽晶杆上的晶体，再以温度3℃/h的速率降至30℃，即获得尺寸为12mm×13mm×16mm的CsB4O6F非线性光学晶体。
实施例12
高温熔液法合成CsB4O6F非线性光学晶体：
依据实施例2得到的化合物CsB4O6F与助熔剂为PbF2按摩尔比1∶0.5混合，放入单晶生长炉中，以温度45℃/h的速率升温至700℃，恒温15小时，得到混合熔液；
制备籽晶：将制得的混合熔液置于单晶炉中，以温度5℃/h的速率降温至610℃，以温度0.6℃/h的速率降温至385℃，再以温度10℃/h的速率降至30℃，得到CsB4O6F晶体的籽晶；
生长晶体：将得到的CsB4O6F籽晶固定于籽晶杆上，从装有制得的混合熔液的晶体生长炉顶部将籽晶下降至液面上方1mm，预热25分钟，然后使籽晶与液面接触，以温度2℃/h的速率降温至晶体生长结束，提出籽晶杆上的晶体，再以温度10℃/h的速率降至30℃，即获得尺寸为15mm×17mm×18mm的CsB4O6F非线性光学晶体。
实施例13
高温熔液法合成CsB4O6F非线性光学晶体：
将依据实施例3得到的化合物CsB4O6F与助熔剂为B2O3按摩尔比1∶0.5混合装入洗净的铂金坩埚，放入单晶生长炉中，以温度40℃/h的速率升温至690℃，恒温10小时，得到混合熔液；
制备籽晶：将制得的混合熔液置于单晶炉中，以温度3℃/h的速率降温至580℃，以温度0.6℃/h的速率降温至330℃，再以温度8℃/h的速率降至30℃，得到CsB4O6F晶体的籽晶；
生长晶体：将得到的CsB4O6F籽晶固定于籽晶杆上，从装有制得的混合熔液的晶体生长炉顶部将籽晶下降至液面上方1mm，预热20分钟，然后使籽晶与液面接触，以温度0.3℃/h的速率降温至晶体生长结束，提出籽晶杆上的晶体，以温度8℃/h的速率降至30℃，即获得尺寸为12mm×15mm×19mm的CsB4O6F非线性光学晶体。
实施例14
高温熔液法合成CsB4O6F非线性光学晶体：
依据实施例4得到的化合物CsB4O6F与助熔剂为PbO按摩尔比1∶0.2混合装入铂金坩埚，放入单晶生长炉中，以温度35℃/h的速率升温至660℃，恒温8小时，得到混合熔液；
制备籽晶：将制得的混合熔液置于单晶炉中，以温度2℃/h的速率降温至575℃，以温度0.2℃/h的速率降温至380℃，再以温度7℃/h的速率降至30℃，得到CsB4O6F籽晶；
生长晶体：将得到的CsB4O6F籽晶固定于籽晶杆上，从装有制得的混合熔液的晶体生长炉顶部将籽晶下降至液面上方1mm，预热25分钟，然后使籽晶与液面接触，以温度0.1℃/h的速率降温至晶体生长结束，提出籽晶杆上的晶体，以温度7℃/h的速率降至30℃，即获得尺寸为10mm×12mm×15mm的CsB4O6F非线性光学晶体。
实施例15
高温熔液法合成CsB4O6F非线性光学晶体：
按摩尔比CsF:H3BO3＝1:4称取原料，与助熔剂为H3BO3按摩尔比1∶0.4混合装入铂金坩埚，放入单晶生长炉中，以温度37℃/h的速率升温至665℃，恒温7小时，得到混合熔液；
制备籽晶：将制得的混合熔液置于单晶炉中，以温度2.4℃/h的速率降温至570℃，以温度0.15℃/h的速率降温至385℃，再以温度7.5℃/h的速率降至30℃，得到CsB4O6F籽晶；
生长晶体：将得到的CsB4O6F籽晶固定于籽晶杆上，从装有制得的混合熔液的晶体生长炉顶部将籽晶下降至液面上方1mm，预热20分钟，然后使籽晶与液面接触，以温度0.15℃/h的速率降温至晶体生长结束，提出籽晶杆上的晶体，再以温度7.5℃/h的速率降至30℃，即获得尺寸为13mm×14mm×16mm的CsB4O6F非线性光学晶体。
实施例16
真空封装法生长CsB4O6F晶体：
依据实施例6得到的化合物CsB4O6F与助熔剂为B2O3按摩尔比1∶0.1混合，装入Φ40mm的石英管中，将石英管抽真空，真空度达到1×10-3Pa，用火焰枪真空封装，放入马弗炉中，以温度10℃/h的速率升温至400℃，恒温3小时，然后以温度0.5℃/天的速率降温至330℃，再以温度2℃/h的速率降至30℃，切开石英管，即获得尺寸为13mm×16mm×21mm的CsB4O6F非线性光学晶体。
实施例17
真空封装法生长CsB4O6F晶体：
将依据实施例7得到的化合物CsB4O6F与助熔剂为CsF按摩尔比1∶1混合，装入Φ40mm的石英管中，将石英管抽真空，真空度达到1×10-3Pa，用火焰枪真空封装，放入马弗炉中，以温度50℃/h的速率升温至700℃，恒温96小时，然后以温度1.5℃/天的速率降温至450℃，再以温度5℃/h的速率降至30℃，切开石英管，即获得尺寸为15mm×18mm×23mm的CsB4O6F非线性光学晶体。
实施例18
真空封装法生长CsB4O6F晶体：
将依据实施例8得到的化合物CsB4O6F与助熔剂为H3BO3按摩尔比1∶0.3混合，装入Φ40mm的石英管中，将石英管抽真空，真空度达到1×10-3Pa，用火焰枪真空封装，放入马弗炉中，以温度35℃/h的速率升温至500℃，恒温50小时，然后以温度0.5℃/天的速率降温至430℃，再以温度4℃/h的速率降至30℃，切开石英管，即获得尺寸为14mm×16mm×17mm的CsB4O6F非线性光学晶体。
实施例19
真空封装法生长CsB4O6F晶体：
将依据实施例9得到的化合物CsB4O6F与助熔剂为PbO按摩尔比1∶0.4混合，装入Φ40mm的石英管中，将石英管抽真空，真空度达到1×10-3Pa，用火焰枪真空封装，放入马弗炉中，以温度32℃/h的速率升温至520℃，恒温52小时，然后以温度0.8℃/天的速率降温至435℃，再以温度4.5℃/h的速率降至30℃，切开石英管，即获得尺寸为14mm×16mm×17mm的CsB4O6F非线性光学晶体。
实施例20
真空封装法生长CsB4O6F晶体：
按CsF:H3BO3＝1:4称取原料，得到的化合物CsB4O6F与助熔剂为PbF2按摩尔比1∶0.5混合，装入Φ40mm的石英管中，将石英管抽真空，真空度达到1×10-3Pa，用火焰枪真空封装，放入马弗炉中，以温度37℃/h的速率升温至510℃，恒温96小时，然后以温度1.2℃/天的速率降温至445℃，再以温度3.5℃/h的速率降至30℃，切开石英管，即获得尺寸为14mm×16mm×17mm的CsB4O6F非线性光学晶体。
实施例21
提拉法合成CsB4O6F非线性光学晶体：
将依据实施例10得到的化合物CsB4O6F装入洗净的铂金坩埚，放入马弗炉中，以温度40℃/h的速率升温至700℃，恒温15小时，得到混合熔体；
将得到的混合熔体以温度5℃/h的速率降温至590℃，以温度2℃/h的速率降温至440℃，再以15℃/h的速率降至30℃，得到CsB4O6F籽晶；
将得到的CsB4O6F籽晶固定于籽晶杆上，从装有制得的混合熔体的晶体生长炉顶部将籽晶下降至液面上方1mm，预热5分钟，然后使籽晶没入液面5mm，通过晶体生长控制仪施加30rpm的晶转，控制温度使熔体饱和，以3mm/天的速度提升籽晶，恒温至晶体生长结束，提出籽晶杆上的晶体，以温度2℃/h的速率降温至440℃，再以温度15℃/h的速率降至30℃，即获得尺寸为12mm×15mm×16mm的CsB4O6F非线性光学晶体。
实施例22
提拉法合成CsB4O6F非线性光学晶体：
依据实施例2得到的化合物CsB4O6F装入铂金坩埚，放入单晶生长炉中，以温度20℃/h的速率升温至400℃，恒温7小时，得到混合熔体；
将得到的混合熔体以温度0.1℃/h的速率降温至400℃，以温度0.2℃/h的速率降温至300℃，再以3℃/h的速率降至30℃，得到CsB4O6F籽晶；
将得到的CsB4O6F籽晶固定于籽晶杆上，从装有制得的熔体的晶体生长炉顶部将籽晶下降至液面上方1mm，预热5分钟，然后使籽晶没入液面1mm，通过晶体生长控制仪施加2rpm的晶转，控制温度使熔体饱和，以1mm/天的速度提升籽晶，恒温至晶体生长结束，提出籽晶杆上的晶体，以温度0.2℃/h的速率降温至300℃，再以温度3℃/h的速率降至30℃，即获得尺寸为11mm×14mm×15mm的CsB4O6F非线性光学晶体。
实施例23
提拉法合成CsB4O6F非线性光学晶体：
按CsF:H3BO3＝1:4称取原料，装入洗净的铂金坩埚，放入马弗炉中，以温度30℃/h的速率升温至650℃，恒温12小时，得到混合熔体；
将得到的混合熔体以温度4℃/h的速率降温至580℃，以温度1℃/h的速率降温至440℃，再以6℃/h的速率降至30℃，得到CsB4O6F籽晶；
将得到的CsB4O6F籽晶固定于籽晶杆上，从装有制得的熔体的晶体生长炉顶部将籽晶下降至液面上方1mm，预热15分钟，然后使籽晶没入液面3mm，通过晶体生长控制仪施加8rpm的晶转，控制温度使熔体饱和，以3mm/天的速度提升籽晶，恒温至晶体生长结束，提出籽晶杆上的晶体，以温度1℃/h的速率降温至440℃，再以温度6℃/h的速率降至30℃，即获得尺寸为17mm×19mm×20mm的CsB4O6F非线性光学晶体。
实施例24
采用坩埚下降法生长CsB4O6F晶体：
依据实施例4得到的化合物CsB4O6F装入铂金坩埚，放入单晶生长炉中，以温度20℃/h的速率升温至700℃，恒温15小时，得到的混合熔体；
将得到的混合熔体以温度5℃/h的速率降温至590℃，以温度2℃/h的速率降温至440℃，再以15℃/h的速率降至30℃，取出铂金坩埚，得到CsB4O6F籽晶；
将得到的籽晶放在铂金坩埚的底部，然后将得到的化合物CsB4O6F放入铂金坩埚中，将铂金坩埚密封并置于坩埚下降炉中，升温至700℃，保温15小时，调整铂金坩埚位置，使接种温度在625℃，再以10mm/天的速度降低铂金坩埚，同时，保持生长温度不变，待生长结束后，以温度2℃/h的速率降温至440℃，再以15℃/h的速率降至30℃，取出铂金坩埚，即得到尺寸为18mm×23mm×24mm的CsB4O6F非线性光学晶体。
实施例25
采用坩埚下降法生长CsB4O6F晶体：
依据实施例5得到的化合物CsB4O6F装入铂金坩埚，放入单晶生长炉中，以温度40℃/h的速率升温至675℃，恒温7小时，得到混合熔体；
将得到的混合熔体以温度0.1℃/h的速率降温至575℃，以温度1.5℃/h的速率降温至380℃，再以12℃/h的速率降至30℃，取出铂金坩埚，得到CsB4O6F籽晶；
将得到的籽晶放在铂金坩埚的底部，然后将得到的化合物CsB4O6F放入铂金坩埚中，将铂金坩埚密封并置于坩埚下降炉中，升温至500℃，保温7小时，调整铂金坩埚位置，使接种温度在500℃，再以1mm/天的速度降低铂金坩埚，同时，保持生长温度不变，待生长结束后，以温度0.2℃/h的速率降温至300℃，再以温度3℃/h的速率降至30℃，取出铂金坩埚，即得到尺寸为19mm×22mm×23mm的CsB4O6F非线性光学晶体。
实施例26
采用坩埚下降法生长CsB4O6F晶体：
按CsF:B2O3＝1:2称取原料，装入铂金坩埚，放入马弗炉中，以温度30℃/h的速率升温至680℃，恒温24小时，得到混合熔体；
将得到的混合熔体以温度3℃/h的速率降温至570℃，以温度1℃/h的速率降温至350℃，再以温度15℃/h的速率降至30℃，取出铂金坩埚，得到CsB4O6F籽晶；
将得到的籽晶放在铂金坩埚的底部，然后将得到的化合物CsB4O6F放入铂金坩埚中，将铂金坩埚密封并置于坩埚下降炉中，升温至680℃，保温12小时，调整铂金坩埚位置，使接种温度在550℃，再以5mm/天的速度降低铂金坩埚，同时，保持生长温度不变，待生长结束后，以温度1℃/h的速率降温至350℃，再以温度15℃/h的速率降至30℃，取出铂金坩埚，即得到尺寸为15mm×16mm×23mm的CsB4O6F非线性光学晶体。
实施例27
泡生法合成CsB4O6F非线性光学晶体：
依据实施例2得到的化合物CsB4O6F装入铂金坩埚，放入单晶生长炉中，以温度40℃/h的速率升温至630℃，恒温18小时，得到混合熔体；
将得到的混合熔体以温度5℃/h的速率降温至565℃，以温度2℃/h的速率降温至380℃，再以温度8℃/h的速率降至30℃，得到CsB4O6F籽晶；
将得到的CsB4O6F籽晶固定于籽晶杆上，从装有制得的熔体的晶体生长炉顶部将籽晶下 降至液面上方1mm，预热60分钟，然后使籽晶浸没液面5mm，以温度0.7℃/h的速率降温，3小时后，将籽晶提升2mm，继续以温度0.7℃/h的速率降温至晶体生长结束，提出籽晶杆上的晶体，以温度2℃/h的速率降温至440℃，再以温度15℃/h的速率降至30℃，即获得尺寸为4mm×6mm×9mm的CsB4O6F非线性光学晶体。
实施例28
泡生法合成CsB4O6F非线性光学晶体：
将依据实施例3得到的化合物CsB4O6F装入铂金坩埚，放入单晶生长炉中，以温度20℃/h的速率升温至640℃，恒温24小时，得到混合熔体；
将得到的混合熔体以温度6℃/h的速率降温至560℃，以温度1.8℃/h的速率降温至390℃，再以温度3.5℃/h的速率降至30℃，得到CsB4O6F籽晶；
用泡生法在化合物熔体中生长晶体：将得到的CsB4O6F籽晶固定于籽晶杆上，从装有制得的熔体的晶体生长炉顶部将籽晶下降至液面上方1mm，预热5分钟，然后使籽晶浸没液面1mm，以温度0.1℃/h的速率降温，10小时后，将籽晶提升1mm，继续以温度0.1℃/h的速率降温至晶体生长结束，提出籽晶杆上的晶体，以温度0.2℃/h的速率降温至300℃，再以温度3℃/h的速率降至30℃，即获得尺寸为13mm×18mm×24mm的CsB4O6F非线性光学晶体。
实施例29
室温溶液法合成CsB4O6F非线性光学晶体：
依据实施例1得到的化合物CsB4O6F放入洗干净的玻璃容器中，加入100mL的去离子水，然后超声波处理5分钟，使其充分混合溶解，然后加入HF和CsOH调节溶液pH值8；
将装有溶液的容器用称量纸封口，放在无晃动、无污染、无空气对流的静态环境中，将封口扎小孔将蒸发速率控制为2mL/天，静置5天；
待溶液在容器底部长出晶体颗粒，直至晶体颗粒大小不再明显变化，生长结束，得到籽晶；
将剩余溶液用定性滤纸将晶粒及溶液中的其它杂质过滤，选择质量较好的籽晶，用铂金丝固定籽晶，将其悬挂于过滤后的溶液中，将封口扎小孔将蒸发速率控制为2mL/天，在室温下静置30天，即获得尺寸为8mm×14mm×17mm的CsB4O6F非线性光学晶体。
实施例30
室温溶液法合成CsB4O6F非线性光学晶体：
按CsF:B2O3＝1:2称取原料，放入洗干净的玻璃容器中，加入20mL的去离子水，然后超声波处理30分钟，使其充分混合溶解，然后加入HF和CsOH调节溶液pH值11；
将装有溶液的容器用称量纸封口，放在无晃动、无污染、无空气对流的静态环境中，将封口扎小孔将蒸发速率控制为0.2mL/天，静置20天；
待溶液在容器底部长出晶体颗粒，直至晶体颗粒大小不再明显变化，生长结束，得到籽晶；
将剩余溶液用定性滤纸将晶粒及溶液中的其它杂质过滤，用铂金丝固定籽晶，将其悬挂于过滤后的溶液中，将封口扎小孔将蒸发速率控制为0.2mL/天，在室温下静置30天，即获 得尺寸为4mm×8mm×9mm的CsB4O6F非线性光学晶体。
实施例31
水热法合成CsB4O6F非线性光学晶体：
依据实施例1得到的化合物CsB4O6F置入5mL去离子水，将不完全溶解的混合物在温度为20℃下的超声波中处理5分钟，使其充分混合；
将混合溶液转入到干净、无污染的体积为100mL的高压反应釜的内衬中，并将反应釜旋紧密封；
将高压反应釜放置在恒温箱内，按温度50℃/h的速率升温至350℃，恒温3天，再以温度5℃/天的降温速率降至室温，打开高压反应釜，即获得尺寸为8mm×9mm×15mm的CsB4O6F非线性光学晶体。
实施例32
水热法合成CsB4O6F非线性光学晶体：
按CsF:H3BO3＝1:4称取原料，置入30mL去离子水，将不完全溶解的混合物在温度为50℃下的超声波中处理30分钟，使其充分混合；
将混合溶液转入到干净、无污染的体积为100mL的高压反应釜的内衬中，并将反应釜旋紧密封；
将高压反应釜放置在恒温箱内，按温度5℃/h的速率升温至150℃，恒温15天，再以温度30℃/天的降温速率降至室温，打开高压反应釜，即获得尺寸为22mm×24mm×27mm的CsB4O6F非线性光学晶体。
实施例33
水热法合成CsB4O6F非线性光学晶体：
依据实施例2得到的化合物CsB4O6F置入8mL去离子水，将不完全溶解的混合物在温度为45℃下的超声波中处理30分钟，使其充分混合；
将混合物转入到干净、无污染的体积为100mL的高压反应釜的内衬中，并将反应釜旋紧密封；
将高压反应釜放置在恒温箱内，按温度40℃/h的速率升温至330℃，恒温10天，再以温度8℃/天的降温速率降至室温，打开高压反应釜，即获得尺寸为12mm×18mm×20mm的CsB4O6F非线性光学晶体。
实施例34
将实施例1-33所得的任意CsB4O6F晶体按相匹配方向加工，按附图3所示安置在3的位置上，在室温下，用调Q-Nd:YAG激光器作光源，入射波长为1064nm，由调Q-Nd:YAG激光器1发出波长为1064nm的红外光束2射入CsB4O6F单晶3，产生波长为532nm的绿色倍频光，输出强度约为同等条件KDP的2倍。
实施例35
将实施例1-33所得的任意CsB4O6F晶体按相匹配方向加工，按附图3所示安置在3的位置上，在室温下，用调Q Nd:YAG激光器作光源，入射波长为532nm，由调Q的Nd:YAG激 光器1发出波长为532nm的红外光束2射入CsB4O6F单晶3，产生波长为266nm的倍频光，输出强度约为同等条件BBO的0.5倍。
实施例36
将实施例1-33所得的任意CsB4O6F晶体按相匹配方向加工，按附图3所示安置在3的位置上，在室温下，用调Q-Nd:YAG激光器作光源，入射波长为355nm，由调Q-Nd:YAG激光器1发出波长为355nm的红外光束2射入CsB4O6F单晶3，可观察到波长为177.3nm的深紫外倍频光输出。

Claims (7)

  1. 一种化合物氟硼酸铯，其特征在于该化合物的化学式为CsB4O6F，分子量为291.15，该化合物为晶体结构。
  2. 一种权利要求1所述的化合物氟硼酸铯的制备方法，其特征在于采用固相合成法或真空封装法制备化合物，具体操作按下列步骤进行：
    所述固相合成法制备化合物氟硼酸铯：
    将含Cs化合物、含B化合物和含F化合物按摩尔比Cs∶B∶F＝0.5-2∶3-5∶0.5-2混合均匀，装入铂金坩埚中，然后放入马弗炉，升温至350-600℃，恒温3-96小时，即得到化合物CsB4O6F；所述含Cs化合物为Cs2CO3、CsNO3、CsHCO3、CsF或CsBF4；含F为化合物CsF或CsBF4；含B化合物为H3BO3、B2O3或CsBF4；
    所述真空封装法制备化合物氟硼酸铯：
    将含Cs化合物、含B化合物和含F化合物按摩尔比Cs∶B∶F＝0.5-2∶3-5∶0.5-2混合均匀，装入Φ40mm的石英管中，将石英管抽真空，真空度达到1×10-3Pa，高温密封，放入马弗炉中，以10-50℃的速率升温至350-600℃，恒温3-96小时，即得到化合物CsB4O6F。所述含Cs化合物为Cs2CO3、CsNO3、CsHCO3、CsF或CsBF4；含F为化合物CsF或CsBF4；含B化合物为H3BO3、B2O3或CsBF4。
  3. 一种氟硼酸铯非线性光学晶体，其特征在于该晶体的化学式为CsB4O6F，分子量为291.15，晶体属正交晶系，空间群为Pna21，晶胞参数为
    Figure PCTCN2017092331-appb-100001
    α＝β＝γ＝90°，单胞体积为
    Figure PCTCN2017092331-appb-100002
  4. 一种权利要求3所述的氟硼酸铯非线性光学晶体的制备方法，其特征在于采用熔体法，高温熔液法，真空封装法，水热法或室温溶液法生长晶体；
    所述熔体法生长氟硼酸铯非线性光学晶体的具体操作按下列步骤进行：
    a、将含Cs化合物、含B化合物和含F化合物按摩尔比Cs∶B∶F＝0.5-2∶3-5∶0.5-2混合均匀，装入铂金坩埚，然后放入马弗炉，升温至350-600℃，恒温3-96小时，即得到化合物CsB4O6F多晶粉末，所述含Cs化合物为Cs2CO3、CsNO3、CsHCO3、CsF或CsBF4；含F为化合物CsF或CsBF4；含B化合物为H3BO3、B2O3或CsBF4；
    b、将得到的化合物CsB4O6F多晶粉末装入洗净的铂金坩埚中，放入马弗炉中，以温度20-40℃/h的速率升温至400-700℃，恒温7-15小时，得到混合熔体；所述含Cs化合物为Cs2CO3、CsNO3、CsHCO3、CsF或CsBF4；含F为化合物CsF或CsBF4；含B化合物为H3BO3、B2O3或CsBF4；
    c、将步骤b的混合熔体以温度0.1-5℃/h降温速率降至400-590℃，以温度0.2-2℃/h的速率降温至300-440℃，再以温度3-15℃/h降温速率降至30℃，得到CsB4O6F籽晶；
    d、采用提拉法在化合物熔体中生长晶体：将步骤c得到的籽晶固定于籽晶杆上，从步骤b制得的熔体的晶体生长炉顶部将籽晶下降至液面上方1mm，预热5-60分钟，然后使籽晶没入液面1-5mm，通过晶体生长控制仪施加2-30rpm的晶转，控制温度使熔体饱和，以1-3mm/天的速度提升籽晶，恒温至晶体生长结束，提出籽晶杆上的晶体，以温度0.2-2℃/h的速率降温至300-440℃，再以温度3-15℃/h的速率降至30℃，即得到CsB4O6F非线性光学晶体；
    或用泡生法在化合物熔体中生长晶体：将步骤c得到的籽晶固定于籽晶杆上，从步骤b制得的熔体的晶体生长炉顶部将籽晶下降至液面上方1mm，预热5-60分钟，然后使籽晶没入液面1-5mm，以温度0.1-0.7℃/h的速率降温，3-10小时后，将籽晶提升1-2mm，继续以温度0.1-0.7℃/h的速率降温至晶体生长结束，提出籽晶杆上的晶体，以温度0.2-2℃/h的速率降温至300-440℃，再以温度3-15℃/h的速率降至30℃，即得到CsB4O6F非线性光学晶体；
    或用坩埚下降法在化合物熔体中生长晶体：先将步骤c制备的籽晶放在坩埚底部，然后再将步骤a制备的化合物CsB4O6F多晶放入坩埚中，将铂金坩埚密封，将生长炉温度升高至500-700℃，恒温7-15小时，调整坩埚位置，使接种温度在500-625℃，再以1-10mm/天的速度降低坩埚，同时，保持生长温度不变，待生长结束后，以温度0.2-2℃/h的降温速率降至300-440℃，再以温度3-15℃/h的速率降至30℃，取出铂金坩埚，即得到CsB4O6F非线性光学晶体；
    所述高温熔液法生长氟硼酸铯非线性光学晶体的具体操作按下列步骤进行：
    a、将含Cs化合物、含B化合物和含F化合物按摩尔比Cs∶B∶F＝0.5-2∶3-5∶0.5-2混合均匀，装入铂金坩埚，然后放入马弗炉，升温至350-600℃，恒温3-96小时，即得到化合物CsB4O6F多晶粉末，所述含Cs化合物为Cs2CO3、CsNO3、CsHCO3、CsF或CsBF4；含F为化合物CsF或CsBF4；含B化合物为H3BO3、B2O3或CsBF4；
    b、将步骤a得到的化合物CsB4O6F多晶粉末与助熔剂按摩尔比1∶0.1-0.5混合均匀，再装入洗净的铂金坩埚中，以温度35-45℃/h的速率升温至400-700℃，恒温7-15小时，得到混合熔液；所述含Cs化合物为Cs2CO3、CsNO3、CsHCO3、CsF或CsBF4；含F为化合物CsF或CsBF4；含B化合物为H3BO3、B2O3或CsBF4；所述助熔剂为CsF，H3BO3，B2O3，PbO或PbF2；
    c、制备籽晶：将步骤b制得的混合熔液置于单晶炉中，然后以温度0.1-5℃/h降温速率降至350-610℃，以温度0.2-0.6℃/h的速率降温至300-385℃，再以温度3-10℃/h的降 温速率降至30℃，得到CsB4O6F的籽晶；
    d、生长晶体：将得到的CsB4O6F籽晶固定于籽晶杆上，从步骤b制得的混合熔液的晶体生长炉顶部将籽晶下降至液面上方1mm，预热10-25分钟，然后使籽晶与液面接触，以温度0.1-2℃/h的速率降温至晶体生长结束，将晶体提离熔液表面，然后以温度3-10℃/h的速率降温至30℃，即得到CsB4O6F非线性光学晶体；
    所述真空封装法生长氟硼酸铯非线性光学晶体的具体操作按下列步骤进行：
    a、将含Cs化合物、含B化合物和含F化合物按摩尔比Cs∶B∶F＝0.5-2∶3-5∶0.5-2混合均匀，装入铂金坩埚中，然后放入马弗炉，以温度10-50℃的速率升至温度350-600℃，恒温3-96小时，得到化合物CsB4O6F多晶粉末，所述含Cs化合物为Cs2CO3、CsNO3、CsHCO3、CsF或CsBF4；含F为化合物CsF或CsBF4；含B化合物为H3BO3、B2O3或CsBF4；
    b、将步骤a得到的化合物CsB4O6F多晶粉末与助熔剂按摩尔比1∶0.1-1混合均匀，再装入石英管中，以温度10-50℃/h的速率升温至400-700℃，恒温3-96小时，然后以温度0.5-1.5℃/天的速率降温至330-450℃，再以温度2-5℃/h的速率降至30℃，切开石英管，即得到CsB4O6F非线性光学晶体，所述含Cs化合物为Cs2CO3、CsNO3、CsHCO3、CsF或CsBF4；含F为化合物CsF、CsBF4或HF；含B化合物为H3BO3、B2O3或CsBF4；所述助熔剂为CsF，H3BO3，B2O3，PbO或PbF2；
    所述水热法生长氟硼酸铯非线性光学晶体的具体操作按下列步骤进行：
    a、将含Cs化合物、含B化合物和含F化合物按摩尔比Cs∶B∶F＝0.5-2∶3-5∶0.5-2混合均匀，装入铂金坩埚中，然后放入马弗炉，升至温度350-600℃，恒温3-96小时，得到产物CsB4O6F多晶粉末，所述含Cs化合物Cs2CO3、CsNO3、CsHCO3、CsF或CH3COOCs；含F化合物CsF或HF；含B化合物H3BO3和B2O3；
    b、将步骤a得到的化合物CsB4O6F多晶粉末，置入5-30mL去离子水中溶解，将不完全溶解的混合物在温度20-50℃下的超声波处理5-30分钟使其充分混合溶解；
    c、将步骤b得到的混合溶液转入到干净、无污染的体积为100mL的高压反应釜的内衬中，并将反应釜旋紧密封；
    d、将高压反应釜放置在恒温箱内，以温度5-50℃/h的速率升温至150-350℃，恒温3-15天，再以温度5-30℃/天的降温速率降至室温，即得到CsB4O6F非线性光学晶体；
    所述室温溶液法生长氟硼酸铯非线性光学晶体的具体操作按下列步骤进行：
    a、将含Cs化合物、含B化合物和含F化合物按摩尔比Cs∶B∶F＝0.5-2∶3-5∶0.5-2混合均匀，装入铂金坩埚中，然后放入马弗炉，升至温度350-600℃，恒温3-96小时，得到产物CsB4O6F多晶粉末，所述含Cs化合物Cs2CO3、CsNO3、CsHCO3、CsF或CH3COOCs；含F 化合物CsF或HF；含B化合物H3BO3和B2O3；
    b、将步骤a得到的化合物CsB4O6F多晶粉末，放入洗干净的玻璃容器中，加入20-100mL的去离子水，然后超声波处理5-60分钟，使其充分混合溶解，然后加入HF和CsOH调节溶液pH值8-11；
    c、将步骤b中装有溶液的容器用称量纸封口，放在无晃动、无污染、无空气对流的静态环境中，将封口扎小孔将蒸发速率控制为0.2-2mL/天，在室温下静置5-20天；
    d、待步骤c中的溶液在容器底部长出晶体颗粒，直至晶体颗粒大小不再明显变化，生长结束，得到籽晶；
    e、将剩余溶液用定性滤纸将晶粒及溶液中的其它杂质过滤，选择质量较好的籽晶，用铂金丝固定籽晶，将其悬挂于过滤后的溶液中，将封口扎小孔将蒸发速率控制为0.2-2mL/天，在室温下静置生长10-30天，得到CsB4O6F非线性光学晶体。
  5. 一种权利要求3所述的氟硼酸铯非线性光学晶体在制备Nd:YAG激光器所输出的1064nm的基频光进行2倍频、3倍频、4倍频、5倍频或6倍频的谐波光输出的用途。
  6. 一种权利要求3所述的氟硼酸铯非线性光学晶体在制备产生低于200nm的深紫外倍频光输出中的用途。
  7. 一种权利要求3所述的化合物氟硼酸铯非线性光学晶体在制备倍频发生器、上或下频率转换器或光参量振荡器中的用途。
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