Compound tin boron oxygen bromine, tin boron oxygen bromine nonlinear optical crystal, preparation method and application
阅读说明：本技术 化合物锡硼氧溴和锡硼氧溴非线性光学晶体及制备方法和用途 (Compound tin boron oxygen bromine, tin boron oxygen bromine nonlinear optical crystal, preparation method and application ) 是由 潘世烈 郭靖宇 韩树娟 于浩海 于 2020-06-02 设计创作，主要内容包括：本发明提供一种化合物锡硼氧溴和锡硼氧溴非线性光学晶体的制备方法和用途,所述化合物的化学式为Sn<Sub>2</Sub>B<Sub>5</Sub>O<Sub>9</Sub>Br,分子量为515.37,采用固相合成法或真空封装法制成；该晶体的化学式为Sn<Sub>2</Sub>B<Sub>5</Sub>O<Sub>9</Sub>Br,分子量为515.37,属于正交晶系,空间群为<I>Pnn</I>2,晶胞参数为<I>a</I>=11.398(4)?,<I>b</I>=11.446(4)?,<I>c</I>=6.553(2)?,单胞体积为854.9(5)?<Sup>3</Sup>,晶体的粉末倍频效应约为KH<Sub>2</Sub>PO<Sub>4</Sub>(KDP)的2.4倍,紫外截止边约为330 nm。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,该晶体的化学稳定性好,可作为短波长非线性光学晶体在全固态激光器中获得应用。(The invention provides a preparation method and application of a compound of stannum boron oxygen bromine and stannum boron oxygen bromine nonlinear optical crystalThe chemical formula of the compound is Sn 2 B 5 O 9 Br with molecular weight of 515.37, and is prepared by solid phase synthesis or vacuum packaging; the chemical formula of the crystal is Sn 2 B 5 O 9 Br, molecular weight of 515.37, belonging to orthorhombic system, space group of Pnn 2, unit cell parameter of a =11.398(4)Å， b =11.446(4)Å， c =6.553(2) Å, unit cell volume 854.9(5) Å 3 The powder frequency doubling effect of the crystal is about KH 2 PO 4 (KDP) 2.4 times the UV cut-off of 330 nm. The crystal is grown by a melt method, a high-temperature melt method, a vacuum packaging method, a hydrothermal method or a room-temperature solution method, has good chemical stability, and can be used as a short-wavelength nonlinear optical crystal to be applied to an all-solid-state laser.)
1. A compound Sn-B-O-Br is characterized in that the chemical formula of the compound is Sn2B5O9Br with molecular weight of 515.37, and is prepared by solid phase synthesis or vacuum packaging.
2. The preparation method of the compound tin boron oxygen bromine as claimed in claim 1, which is characterized by adopting a solid phase synthesis method or a vacuum packaging method, and comprises the following steps:
the solid-phase synthesis method is used for preparing a compound of tin, boron, oxygen and bromine:
uniformly mixing Sn-containing compound, B-containing compound and Br-containing compound according to the molar ratio of Sn to B to Br of 2 to 5 to 1, placing the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, heating the mixture to 300 ℃ and 500 ℃ in vacuum or inert atmosphere, and keeping the temperature for 24 to 120 hours to obtain the Sn compound2B5O9Br, wherein the Sn-containing compound is SnO or SnBr2Or SnB4O7(ii) a The compound containing B is H3BO3、B2O3Or SnB4O7(ii) a Containing Br as compound SnBr2；
The vacuum packaging method is used for preparing a compound of tin, boron, oxygen and bromine:
a Sn-containing compound, a Sn-containing compoundMixing the compound B and the compound containing Br at a molar ratio of Sn to B to Br of 2 to 5 to 1, placing the mixture into a quartz tube, and vacuumizing the quartz tube until the vacuum degree reaches 1 × 10−3Pa, sealing at high temperature, placing in a muffle furnace, heating to 300-500 ℃ at the speed of 5-10 ℃/h, and keeping the temperature for 24-120 hours to obtain a compound Sn2B5O9Br, wherein the Sn-containing compound is SnO or SnBr2Or SnB4O7(ii) a The compound containing B is H3BO3、B2O3Or SnB4O7(ii) a Containing Br as compound SnBr2。
3. A tin-boron-oxygen-bromine nonlinear optical crystal is characterized in that the chemical formula of the crystal is Sn2B5O9Br, molecular weight of 515.37, belonging to orthorhombic system, space group ofPnn2, unit cell parameter ofa= 11.398(4) Å，b=11.446(4) Å，c=6.553(2) Å, unit cell volume 854.9(5) Å3。
4. A method for preparing the Sn-B-O-Br nonlinear optical crystal as claimed in claim 3, characterized in that the crystal is grown by a melt method, a high-temperature melt method, a vacuum encapsulation method, a hydrothermal method or a room-temperature solution method;
the specific operation of growing the tin-boron-oxygen-bromine nonlinear optical crystal by the melt method is carried out according to the following steps:
a. uniformly mixing Sn-containing compound, B-containing compound and Br-containing compound according to the molar ratio of Sn to B to Br of 2 to 5 to 1, placing the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, heating the mixture to 300 ℃ and 500 ℃ in a vacuum or inert atmosphere, and keeping the temperature for 24 to 120 hours to obtain Sn2B5O9Br polycrystalline powder, wherein the Sn-containing compound is SnO or SnBr2Or SnB4O7(ii) a The compound containing B is H3BO3、B2O3Or SnB4O7(ii) a Containing Br as compound SnBr2；
b. Sn prepared in the step a2B5O9The Br polycrystalline powder is filled into a platinum crucible and placedHeating to 650-750 ℃ in a muffle furnace in vacuum or inert atmosphere, and keeping the temperature for 10-120 hours to obtain a mixed melt;
c. c, slowly reducing the mixed melt obtained in the step b to 350 ℃ at the speed of 0.2-3 ℃/h, and rapidly reducing the temperature to room temperature at the speed of 2-5 ℃/h to obtain Sn2B5O9Br seed crystal;
d. adopting a pulling method to grow crystals in a compound melt: fixing the seed crystal obtained in the step c on a seed crystal rod, placing the seed crystal under vacuum or inert atmosphere, placing the seed crystal from the upper part of the mixed melt prepared in the step b, applying crystal rotation of 2-15rpm through a crystal growth controller, pulling the seed crystal at the speed of 1-8 mm/day, simultaneously cooling at the speed of 0.1-5 ℃/h, and obtaining the Sn-B-O-Br Sn after crystal growth is stopped2B5O9Br nonlinear optical crystal;
or growing crystals in a compound melt by using a kyropoulos method: c, fixing the seed crystal obtained in the step c on a seed crystal rod, placing the seed crystal under vacuum or inert atmosphere, lowering the seed crystal from the upper part of the melt prepared in the step b, cooling at the speed of 0.1-10 ℃/h to grow the crystal for 5-15 hours, slowly lifting the crystal, continuing to grow without departing from the liquid level, repeating the steps, and obtaining the Sn-B-O-Br Sn after the growth of the crystal is stopped2B5O9Br nonlinear optical crystal;
or growing the crystal in a compound melt by adopting a Bridgman method: placing the seed crystal prepared in the step c at the bottom of the crucible, and then placing the compound Sn prepared in the step a2B5O9Putting Br polycrystalline powder into a crucible, sealing the platinum crucible, keeping the crucible in vacuum or inert atmosphere, raising the temperature of a growth furnace to 700 ℃ plus materials, keeping the temperature constant for 10-120 hours, adjusting the position of the crucible to slightly melt seed crystals, then reducing the crucible at the speed of 1-10 mm/day, keeping the growth temperature unchanged, or reducing the temperature to 400 ℃ at the fastest speed of 3 ℃/h, and after the growth is finished, rapidly reducing the temperature to room temperature at the speed of 5-10 ℃/h to obtain the Sn-B-O-Br Sn2B5O9Br nonlinear optical crystal;
the specific operation of growing the tin-boron-oxygen-bromine nonlinear optical crystal by the high-temperature liquid-melt method is carried out according to the following steps:
a. uniformly mixing Sn-containing compound, B-containing compound and Br-containing compound according to the molar ratio of Sn to B to Br of 2 to 5 to 1, placing the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace in vacuum or inert atmosphere, keeping the temperature at 500 ℃ for 24 to 120 hours to obtain Sn2B5O9Br polycrystalline powder, wherein the Sn-containing compound is SnO or SnBr2Or SnB4O7(ii) a The compound containing B is H3BO3、B2O3Or SnB4O7(ii) a Containing Br as compound SnBr2；
b. The compound Sn obtained in the step a2B5O9Uniformly mixing Br polycrystalline powder and a fluxing agent according to the mol ratio of 1: 0.1-6, then placing the mixture into a platinum crucible, placing the platinum crucible in vacuum or inert atmosphere, heating to 500-800 ℃, and keeping the temperature for 5-120 hours to obtain a mixed melt; wherein the fluxing agent is SnBr2、H3BO3Or B2O3；
c. Preparing seed crystals: placing the mixed melt obtained in the step b in a single crystal furnace, placing the single crystal furnace in vacuum or inert atmosphere, slowly cooling to 400 ℃ at the speed of 0.1-2 ℃/h, and then rapidly cooling to room temperature at the speed of 5-10 ℃/h to obtain Sn2B5O9Br seed crystal;
d. growing a crystal: fixing the seed crystal obtained in the step c on a seed crystal rod, placing the seed crystal under vacuum or inert atmosphere, placing the seed crystal from the upper part of the mixed melt prepared in the step b, applying crystal rotation of 2-20rpm through a crystal growth controller, cooling at the speed of 0.1-3 ℃/h, and obtaining the Sn-B-O-Br Sn after the crystal growth stops2B5O9Br nonlinear optical crystal;
the specific operation of growing the tin-boron-oxygen-bromine nonlinear optical crystal by the vacuum packaging method is carried out according to the following steps:
a. uniformly mixing Sn-containing compound, B-containing compound and Br-containing compound according to the molar ratio of Sn to B to Br of 2 to 5 to 1, placing the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace in vacuum or inert atmosphere, keeping the temperature at 500 ℃ for 24 to 120 hours to obtain the Sn-containing compound2B5O9Br polycrystalline powder, wherein the Sn-containing compound is SnO or SnBr2Or SnB4O7(ii) a The compound containing B is H3BO3、B2O3Or SnB4O7(ii) a Containing Br as compound SnBr2；
b. The compound Sn obtained in the step a2B5O9Uniformly mixing Br polycrystalline powder and a fluxing agent according to the mol ratio of 0-1: 0.1-6, placing the mixture into a quartz tube, placing the quartz tube into a muffle furnace after high-temperature sealing, heating to 500-800 ℃, keeping the temperature for 24-120 hours, then cooling to 350 ℃ at the speed of 0.1-3 ℃/h, and then rapidly cooling to room temperature at the speed of 5-10 ℃/h to obtain the Sn-B-O-Br Sn2B5O9Br nonlinear optical crystal, wherein the fluxing agent is SnBr2，H3BO3Or B2O3；
The specific operation of growing the tin-boron-oxygen-bromine nonlinear optical crystal by the hydrothermal method is carried out according to the following steps:
a. uniformly mixing Sn-containing compound, B-containing compound and Br-containing compound according to the molar ratio of Sn to B to Br of 2 to 5 to 1, placing the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, and keeping the temperature at 300-500 ℃ for 24-120 hours under vacuum or inert atmosphere to obtain the Sn compound2B5O9Br polycrystalline powder, the Sn-containing compound is SnO or SnBr2Or SnB4O7(ii) a The compound containing B is H3BO3、B2O3Or SnB4O7(ii) a Containing Br as compound SnBr2；
b. The compound Sn obtained in the step a2B5O9Dissolving Br polycrystalline powder in deionized water, ultrasonic treating the incompletely dissolved mixture at 60 deg.C to make it fully mixed and dissolved, adding HBr and NH3·H2Adjusting the pH value to 8-11 by O;
c. b, transferring the mixed solution obtained in the step b into a clean and pollution-free lining of a high-pressure reaction kettle with the volume of 100mL, and screwing and sealing the reaction kettle;
d. placing the high-pressure reaction kettle in a constant temperature box, heating to 150-,keeping the temperature for 5 to 8 days, and then cooling to room temperature at a cooling rate of 5 to 20 ℃/day to obtain the Sn-B-O-Br Sn2B5O9Br nonlinear optical crystal;
the room temperature solution method is used for growing Sn-B-O-Br Sn2B5O9The specific operation of the Br nonlinear optical crystal is carried out according to the following steps:
a. uniformly mixing Sn-containing compound, B-containing compound and Br-containing compound according to the molar ratio of Sn to B to Br of 2 to 5 to 1, placing the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, and keeping the temperature at 300-500 ℃ for 24-120 hours to obtain the Sn-containing compound2B5O9Br polycrystalline powder, the Sn-containing compound is SnO or SnBr2Or SnB4O7(ii) a The compound containing B is H3BO3、B2O3Or SnB4O7(ii) a Containing Br as compound SnBr2；
b. The compound Sn obtained in the step a2B5O9Putting Br polycrystalline powder into a cleaned glass container, adding 20-100mL deionized water, then carrying out ultrasonic treatment to fully mix and dissolve, and using HBr and NH3·H2Adjusting the pH value to 8-11 by using O, and filtering by using filter paper to obtain a mixed solution;
c. b, placing the mixed solution obtained in the step b into a clean glass container, sealing the container by using weighing paper, placing the container in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the seal to adjust the evaporation rate of water in the water solution, and standing the container for 5 to 20 days at room temperature;
d. c, growing crystal particles on the bottom of the container by the solution in the step c until the size of the crystal particles is not obviously changed any more, and obtaining seed crystals;
e. selecting the seed crystal with better quality in the step d, suspending the seed crystal in the mixed solution prepared in the step b, standing and growing for 10-30 days at room temperature to obtain the Sn-B-O-Br Sn2B5O9Br nonlinear optical crystal.
5. Use of the Sn-B-O-Br nonlinear optical crystal of claim 3 in preparation of harmonic light output by 2 frequency doubling of 1064nm fundamental frequency light output by Nd: YAG laser.
6. Use of the tin boron oxygen bromine nonlinear optical crystal of claim 3 in the preparation of a light source that produces a short wavelength doubled light output of 532 nm.
7. Use of a tin boron oxygen bromine nonlinear optical crystal of claim 3 in the preparation of a frequency doubling generator, an upper or lower frequency converter or an optical parametric oscillator.
Technical Field
The invention relates to a compound of stannum boron oxygen bromine and stannum boron oxygen bromine nonlinear optical crystal, a preparation method and application thereof.
Background
The short-wavelength nonlinear optical crystal can convert laser in near infrared, visible and other wave bands into short-wavelength laser by utilizing the frequency conversion property of the short-wavelength nonlinear optical crystal, and has important application value in the fields of medical treatment, communication, scientific research and the like. As is known, the current practical short-wavelength nonlinear optical crystal is KBe invented by Chinese scientists2BO3F2(KBBF) crystals, BaB2O4(BBO) and LiB3O5(LBO), however, these crystals have the defects of difficulty in growing large-size crystals, low rate and the like, and the application thereof is limited to a certain extent. Therefore, the preparation of the novel short-wavelength nonlinear optical crystal material with excellent comprehensive performance has important significance and practical value.
In the previous research, five compounds, namely lead barium bromoborate and lead barium bromoborate nonlinear optical crystals and preparation methods and applications (patent application No. CN201210081872), potassium bromoborate nonlinear optical crystals and preparation methods and applications (patent application No. CN201010250911), barium bromoborate and barium bromoborate nonlinear optical crystals and preparation methods and applications (patent application No. CN201310591017), sodium bromoborate and sodium bromoborate optical crystals and preparation methods and applications (CN201410390210), rubidium sodium bromoborate and rubidium sodium bromoborate optical crystals and preparation methods and applications (patent application No. CN201410390209) are providedThe related patent. The present invention is mainly different from the above five patents in that the compound Sn of the present invention2B5O9The Br space group is Pnn2, belonging to the orthorhombic system. In addition, the growth habit, the key parameters of the growth process, the linear and nonlinear optical properties, the performance and the like of the crystal are different from those of the former.
Patent application No. cn201910921550. application of x tin boron oxy-chlorine birefringent crystal; the patent application No. CN201910166628.1 compound stannum boron oxygen chlorine and stannum boron oxygen chlorine nonlinear optical crystal and the preparation method and application thereof are earlier works of the applicant, and compared with the compound stannum boron oxygen bromine and stannum boron oxygen bromine nonlinear optical crystal and the preparation method and application thereof, although the molecular formulas are similar and the crystal systems and space groups are the same, the crystal structures, the preparation and growth processes, the optical properties and the application thereof are different. Crystal structure aspect: the bond lengths and bond angles of Sn-O, Sn-X (X ═ Cl, Br) and B-O of the tin boron oxygen bromide and tin boron oxygen chloride compounds are different, and the structures determine the properties, so that the growth processes and nonlinear properties of the compounds are different. The preparation and growth process comprises the following steps: due to SnBr2BiSnCl2The tin boron oxy-chlorine is more unstable, so that the preparation and crystal growth of the tin boron oxy-bromine compound are difficult, and the preparation temperature and the crystal growth temperature are different. Nonlinear properties optical properties: under the same condition, the second-order nonlinear effect of the tin boron oxygen bromine is 4.8 times of that of the tin boron oxygen chlorine, and the fundamental reason for the performance gain is caused by the action of Br, which further indicates that although the molecular formulas of the two are similar, the performances are different. Non-linear application areas: due to the fact that the nonlinear effect of the tin-boron-oxygen-bromine is larger, the application range of the tin-boron-oxygen-bromine cut into devices is larger, and the application potential is also larger.
Disclosure of Invention
The invention aims to provide a compound of tin, boron, oxygen and bromine, wherein the chemical formula of the compound is Sn2B5O9Br with molecular weight of 515.37, and is prepared by solid-phase reaction or vacuum packaging.
Another object of the present invention is to provide Sn-B-O-Br Sn2B5O9Br nonlinear optical crystal ofThe chemical formula of the crystal is Sn2B5O9Br, molecular weight 515.37. Belongs to the orthorhombic system, space group is Pnn2, unit cell parameter is Unit cell volume of
It is a further object of the present invention to provide Sn, B, O, and B bromine Sn2B5O9The preparation method of the Br nonlinear optical crystal adopts a melt method, a high-temperature melt method, a vacuum packaging method, a hydrothermal method or a room-temperature solution method to grow the crystal.
It is another object of the present invention to provide Sn-B-O-Br Sn2B5O9Use of a Br nonlinear optical crystal.
The chemical formula of the compound of the invention is Sn2B5O9Br with molecular weight of 515.37, and is prepared by solid phase synthesis or vacuum packaging.
The preparation method of the compound tin boron oxygen bromine adopts a solid phase synthesis method or a vacuum packaging method, and comprises the following specific operation steps:
the solid-phase synthesis method is used for preparing a compound of tin, boron, oxygen and bromine:
uniformly mixing Sn-containing compound, B-containing compound and Br-containing compound according to the molar ratio of Sn to B to Br of 2 to 5 to 1, placing the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, heating the mixture to 300 ℃ and 500 ℃ in vacuum or inert atmosphere, and keeping the temperature for 24 to 120 hours to obtain the Sn compound2B5O9Br, wherein the Sn-containing compound is SnO or SnBr2Or SnB4O7(ii) a The compound containing B is H3BO3、B2O3Or SnB4O7(ii) a Containing Br as compound SnBr2；
The vacuum packaging method is used for preparing a compound of tin, boron, oxygen and bromine:
uniformly mixing Sn-containing compound, B-containing compound and Br-containing compound according to the molar ratio of Sn to B to Br of 2 to 5 to 1, filling the mixture into a quartz tube, vacuumizing the quartz tube, and enabling the vacuum degree to reach 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, heating to 300-500 ℃ at the speed of 5-10 ℃/h, and keeping the temperature for 24-120 hours to obtain a compound Sn2B5O9Br, wherein the Sn-containing compound is SnO or SnBr2Or SnB4O7(ii) a The compound containing B is H3BO3、B2O3Or SnB4O7(ii) a Containing Br as compound SnBr2。
A tin-boron-oxygen-bromine nonlinear optical crystal has a chemical formula of Sn2B5O9Br, molecular weight of 515.37, belonging to orthorhombic system, space group of Pnn2, unit cell parameter ofUnit cell volume of
The preparation method of the tin-boron-oxygen-bromine nonlinear optical crystal adopts a melt method, a high-temperature melt method, a vacuum packaging method, a hydrothermal method or a room-temperature solution method to grow the crystal;
the specific operation of growing the tin-boron-oxygen-bromine nonlinear optical crystal by the melt method is carried out according to the following steps:
a. uniformly mixing Sn-containing compound, B-containing compound and Br-containing compound according to the molar ratio of Sn to B to Br of 2 to 5 to 1, placing the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, heating the mixture to 300 ℃ and 500 ℃ in a vacuum or inert atmosphere, and keeping the temperature for 24 to 120 hours to obtain Sn2B5O9Br polycrystalline powder, wherein the Sn-containing compound is SnO or SnBr2Or SnB4O7(ii) a The compound containing B is H3BO3、B2O3Or SnB4O7(ii) a Containing Br as compound SnBr2；
b. Will be provided withSn prepared in step a2B5O9Putting the Br polycrystalline powder into a platinum crucible, placing the platinum crucible in a muffle furnace, heating to 650 plus 750 ℃ in vacuum or inert atmosphere, and keeping the temperature for 10-120 hours to obtain a mixed melt;
c. c, slowly reducing the mixed melt obtained in the step b to 350 ℃ at the speed of 0.2-3 ℃/h, and rapidly reducing the temperature to room temperature at the speed of 2-5 ℃/h to obtain Sn2B5O9Br seed crystal;
d. adopting a pulling method to grow crystals in a compound melt: fixing the seed crystal obtained in the step c on a seed crystal rod, placing the seed crystal under vacuum or inert atmosphere, placing the seed crystal from the upper part of the mixed melt prepared in the step b, applying crystal rotation of 2-15rpm through a crystal growth controller, pulling the seed crystal at the speed of 1-8 mm/day, simultaneously cooling at the speed of 0.1-5 ℃/h, and obtaining the Sn-B-O-Br Sn after crystal growth is stopped2B5O9Br nonlinear optical crystal;
or growing crystals in a compound melt by using a kyropoulos method: c, fixing the seed crystal obtained in the step c on a seed crystal rod, placing the seed crystal under vacuum or inert atmosphere, lowering the seed crystal from the upper part of the melt prepared in the step b, cooling at the speed of 0.1-10 ℃/h to grow the crystal for 5-15 hours, slowly lifting the crystal, continuing to grow without departing from the liquid level, repeating the steps, and obtaining the Sn-B-O-Br Sn after the growth of the crystal is stopped2B5O9Br nonlinear optical crystal;
or growing the crystal in a compound melt by adopting a Bridgman method: placing the seed crystal prepared in the step c at the bottom of the crucible, and then placing the compound Sn prepared in the step a2B5O9Putting Br polycrystalline powder into a crucible, sealing the platinum crucible, keeping the crucible in vacuum or inert atmosphere, raising the temperature of a growth furnace to 700 ℃ plus materials, keeping the temperature constant for 10-120 hours, adjusting the position of the crucible to slightly melt seed crystals, then reducing the crucible at the speed of 1-10 mm/day, keeping the growth temperature unchanged, or reducing the temperature to 400 ℃ at the fastest speed of 3 ℃/h, and after the growth is finished, rapidly reducing the temperature to room temperature at the speed of 5-10 ℃/h to obtain the Sn-B-O-Br Sn2B5O9Br nonlinear optical crystal;
the specific operation of growing the tin-boron-oxygen-bromine nonlinear optical crystal by the high-temperature liquid-melt method is carried out according to the following steps:
a. uniformly mixing Sn-containing compound, B-containing compound and Br-containing compound according to the molar ratio of Sn to B to Br of 2 to 5 to 1, placing the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace in vacuum or inert atmosphere, keeping the temperature at 500 ℃ for 24 to 120 hours to obtain Sn2B5O9Br polycrystalline powder, wherein the Sn-containing compound is SnO or SnBr2Or SnB4O7(ii) a The compound containing B is H3BO3、B2O3Or SnB4O7(ii) a Containing Br as compound SnBr2；
b. The compound Sn obtained in the step a2B5O9Uniformly mixing Br polycrystalline powder and a fluxing agent according to the mol ratio of 1: 0.1-6, then placing the mixture into a platinum crucible, placing the platinum crucible in vacuum or inert atmosphere, heating to 500-800 ℃, and keeping the temperature for 5-120 hours to obtain a mixed melt; wherein the fluxing agent is SnBr2、H3BO3Or B2O3；
c. Preparing seed crystals: placing the mixed melt obtained in the step b in a single crystal furnace, placing the single crystal furnace in vacuum or inert atmosphere, slowly cooling to 400 ℃ at the speed of 0.1-2 ℃/h, and then rapidly cooling to room temperature at the speed of 5-10 ℃/h to obtain Sn2B5O9Br seed crystal;
d. growing a crystal: fixing the seed crystal obtained in the step c on a seed crystal rod, placing the seed crystal under vacuum or inert atmosphere, placing the seed crystal from the upper part of the mixed melt prepared in the step b, applying crystal rotation of 2-20rpm through a crystal growth controller, cooling at the speed of 0.1-3 ℃/h, and obtaining the Sn-B-O-Br Sn after the crystal growth stops2B5O9Br nonlinear optical crystal;
the specific operation of growing the tin-boron-oxygen-bromine nonlinear optical crystal by the vacuum packaging method is carried out according to the following steps:
a. uniformly mixing Sn-containing compound, B-containing compound and Br-containing compound according to the molar ratio of Sn to B to Br of 2 to 5 to 1, placing the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, and vacuumizingOr under inert atmosphere, at the temperature of 300-500 ℃, keeping the temperature for 24-120 hours to obtain the compound Sn2B5O9Br polycrystalline powder, wherein the Sn-containing compound is SnO or SnBr2Or SnB4O7(ii) a The compound containing B is H3BO3、B2O3Or SnB4O7(ii) a Containing Br as compound SnBr2；
b. The compound Sn obtained in the step a2B5O9Uniformly mixing Br polycrystalline powder and a fluxing agent according to the mol ratio of 0-1: 0.1-6, placing the mixture into a quartz tube, placing the quartz tube into a muffle furnace after high-temperature sealing, heating to 500-800 ℃, keeping the temperature for 24-120 hours, then cooling to 350 ℃ at the speed of 0.1-3 ℃/h, and then rapidly cooling to room temperature at the speed of 5-10 ℃/h to obtain the Sn-B-O-Br Sn2B5O9Br nonlinear optical crystal, wherein the fluxing agent is SnBr2，H3BO3Or B2O3；
The specific operation of growing the tin-boron-oxygen-bromine nonlinear optical crystal by the hydrothermal method is carried out according to the following steps:
a. uniformly mixing Sn-containing compound, B-containing compound and Br-containing compound according to the molar ratio of Sn to B to Br of 2 to 5 to 1, placing the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, and keeping the temperature at 300-500 ℃ for 24-120 hours under vacuum or inert atmosphere to obtain the Sn compound2B5O9Br polycrystalline powder, the Sn-containing compound is SnO or SnBr2Or SnB4O7(ii) a The compound containing B is H3BO3、B2O3Or SnB4O7(ii) a Containing Br as compound SnBr2；
b. The compound Sn obtained in the step a2B5O9Dissolving Br polycrystalline powder in deionized water, ultrasonic treating the incompletely dissolved mixture at 60 deg.C to make it fully mixed and dissolved, adding HBr and NH3·H2Adjusting the pH value to 8-11 by O;
c. b, transferring the mixed solution obtained in the step b into a clean and pollution-free lining of a high-pressure reaction kettle with the volume of 100mL, and screwing and sealing the reaction kettle;
d. placing the high-pressure reaction kettle in a constant temperature box, heating to 150-350 ℃, keeping the temperature for 5-8 days, and cooling to room temperature at a cooling rate of 5-20 ℃/day to obtain the Sn-B-O-Br Sn2B5O9Br nonlinear optical crystal;
the room temperature solution method is used for growing Sn-B-O-Br Sn2B5O9The specific operation of the Br nonlinear optical crystal is carried out according to the following steps:
a. uniformly mixing Sn-containing compound, B-containing compound and Br-containing compound according to the molar ratio of Sn to B to Br of 2 to 5 to 1, placing the mixture into a platinum crucible, placing the platinum crucible into a muffle furnace, and keeping the temperature at 300-500 ℃ for 24-120 hours to obtain the Sn-containing compound2B5O9Br polycrystalline powder, the Sn-containing compound is SnO or SnBr2Or SnB4O7(ii) a The compound containing B is H3BO3、B2O3Or SnB4O7(ii) a Containing Br as compound SnBr2；
b. The compound Sn obtained in the step a2B5O9Putting Br polycrystalline powder into a cleaned glass container, adding 20-100mL deionized water, then carrying out ultrasonic treatment to fully mix and dissolve, and using HBr and NH3·H2Adjusting the pH value to 8-11 by using O, and filtering by using filter paper to obtain a mixed solution;
c. b, placing the mixed solution obtained in the step b into a clean glass container, sealing the container by using weighing paper, placing the container in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the seal to adjust the evaporation rate of water in the water solution, and standing the container for 5 to 20 days at room temperature;
d. c, growing crystal particles on the bottom of the container by the solution in the step c until the size of the crystal particles is not obviously changed any more, and obtaining seed crystals;
e. selecting the seed crystal with better quality in the step d, suspending the seed crystal in the mixed solution prepared in the step b, standing and growing for 10-30 days at room temperature to obtain the Sn-B-O-Br Sn2B5O9Br nonlinear optical crystal.
The tin-boron-oxygen-bromine nonlinear optical crystal is used for 2-frequency-doubled harmonic light output in the preparation of 1064nm fundamental frequency light output by an Nd: YAG laser.
The tin boron oxygen bromine nonlinear optical crystal is used for preparing the optical crystal which generates 532nm short-wavelength frequency doubling light output.
The tin-boron-oxygen-bromine nonlinear optical crystal is used for preparing a frequency doubling generator, an upper or lower frequency converter or an optical parametric oscillator.
The preparation method of the tin-boron-oxygen-bromine nonlinear optical crystal comprises the steps of using a platinum crucible, an iridium crucible, a ceramic crucible, a quartz tube, a conical flask and a beaker as containers in the preparation process, and using a hydrothermal kettle with a polytetrafluoroethylene lining or a stainless steel lining provided with a platinum sleeve as the lining. When the container is a quartz tube, vacuumizing is needed before sealing, so that the quartz tube is prevented from being burst due to volatilization of raw materials in the reaction process. When the container is a conical bottle or a beaker, the container is cleaned by acid, rinsed by deionized water and dried.
According to the preparation method of the tin-boron-oxygen-bromine nonlinear optical crystal, a resistance furnace used in the preparation process is a muffle furnace or a drying oven.
By adopting the preparation method of the tin-boron-oxygen-bromine nonlinear optical crystal, Sn with the size of centimeter level is obtained by the method2B5O9Br nonlinear optical crystal, large size crucible or container and prolonged crystal growth period can obtain Sn of corresponding large size2B5O9The Br nonlinear optical crystal is easy to grow, transparent and free of package in crystal growth, and has the advantages of high growth speed, low cost, easy obtainment of large-size crystals and the like.
The large-size Sn obtained by adopting the preparation method of the tin-boron-oxygen-bromine nonlinear optical crystal2B5O9The Br nonlinear optical crystal is prepared through orienting the blank of crystal according to the crystallographic data, cutting the crystal according to needed angle, thickness and cross-section size, polishing the light passing surface of crystal, and Sn2B5O9The Br nonlinear optical crystal has the advantages of light transmission waveband of about 330nm, stable physical and chemical properties, difficult deliquescence, easy processing and storage and the like.
Drawings
FIG. 1 shows a compound Sn according to the present invention2B5O9Powder XRD spectrum of Br;
FIG. 2 shows Sn according to the present invention2B5O9A structure diagram of a Br nonlinear optical crystal;
FIG. 3 shows Sn according to the present invention2B5O9Working principle diagram of nonlinear optical device made of Br nonlinear crystal, wherein 1 is laser, 2 is hololens, and 3 is Sn2B5O9Br crystal, 4 as beam splitter prism, 5 as filter.
Detailed Description
The present invention is further described with reference to the following examples, which should be construed as limiting the scope of the invention and any modifications made thereto without departing from the spirit of the invention. The raw materials or equipment used in the present invention are commercially available unless otherwise specified.
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