Compound tin boron oxygen bromine and tin boron oxygen bromine birefringent crystal, and preparation method and application thereof
阅读说明：本技术 化合物锡硼氧溴和锡硼氧溴双折射晶体及制备方法和用途 (Compound tin boron oxygen bromine and tin boron oxygen bromine birefringent crystal, and preparation method and application thereof ) 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：本发明涉及一种化合物锡硼氧溴和锡硼氧溴双折射晶体及制备方法和用途,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>,透过范围330–3500nm,双折射率为0.244(3500nm)–0.293(330nm)之间。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,所述的锡硼氧溴双折射晶体具有较大的双折射率,在光学和通讯领域有重要应用,可用于制作偏振分束棱镜,相位延迟器件和电光调制器件,用于红外-可见-紫外波段,为双轴晶体。(Hair brushA compound Sn-B-O-Br and its birefringent crystal, its chemical formula 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 transmission range is 330-3500 nm, and the birefringence is between 0.244(3500nm) -0.293 (330 nm). The tin-boron-oxygen-bromine birefringent crystal has larger birefringence, has important application in the fields of optics and communication, can be used for manufacturing a polarization beam splitter prism, a phase delay device and an electro-optical modulator, is used for infrared-visible-ultraviolet bands, and is a biaxial crystal.)
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:
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。
3. A Sn-B-O-Br birefringent 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 producing a Sn-B-O-Br birefringent crystal according to 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 birefringent 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 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 stopped2B5O9A Br birefringent 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 stopped2B5O9A Br birefringent 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 Sn2B5O9A Br birefringent crystal;
the specific operation of growing the tin-boron-oxygen-bromine birefringent 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: subjecting step c toFixing the seed crystal on a seed crystal rod, placing the seed crystal under vacuum or inert atmosphere, placing the seed crystal above 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 crystal growth is stopped2B5O9A Br birefringent crystal;
the specific operation of growing the tin-boron-oxygen-bromine birefringent 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 birefringent crystal, wherein the flux is SnBr2，H3BO3Or B2O3；
The specific operation of growing the tin-boron-oxygen-bromine birefringent 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 Sn2B5O9A Br birefringent crystal;
the room temperature solution method is used for growing Sn-B-O-Br Sn2B5O9The specific operation of the Br birefringent 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 Sn2B5O9A Br birefringent crystal.
5. Use of a Sn-B-O-Br birefringent crystal of claim 3 in the manufacture of an optical isolator, circulator, beam displacer, optical polarizer or optical modulator.
6. Use according to claim 5, wherein the optical polariser comprises a polarising beam splitter prism.
7. Use according to claim 6, wherein the polarizing beam splitting prism is a Glan prism, Wollaston prism or Rochon prism.
Technical Field
The invention relates to a compound of Sn-B-O-Br and Sn-B-O-Br birefringent crystal, a preparation method and application thereof, in particular to a compound of Sn with a molecular formula for infrared-visible-ultraviolet bands2B5O9Use of tin boron oxygen bromine birefringent crystal of Br.
Background
Birefringence refers to the phenomenon where one light beam is projected onto the surface of a crystal to produce two refracted light beams, the underlying cause of which is the anisotropy of the crystal material. When light propagates in a non-homogeneous body (e.g. a crystal other than a cubic system), its vibration characteristics are changed except in a particular direction (along the optical axis), and the light is decomposed into two polarized lights with different refractive indices and with mutually perpendicular vibration directions of electric field vectors, different propagation speeds, and the phenomenon is called birefringence. The birefringence property of the crystal is an important optical performance parameter of the photoelectric functional material crystal, linearly polarized light can be obtained by utilizing the characteristics of the birefringence crystal, and displacement of light beams and the like are realized, so that the birefringence crystal becomes a key material for manufacturing optical elements such as an optical isolator, a circulator, a light beam shifter, an optical polarizer, an optical modulator and the like. Common birefringent materials are mainly calcite crystals, rutile crystals and LiNbO3Crystal, YVO4Crystal, α -BaB2O4Crystals and MgF2The α -BBO crystal is an excellent birefringent material, has good optical performance and has good transmission from ultraviolet to middle infrared, but the birefringence value ([email protected]) of the crystal is only about 1/2 of YVO4([email protected]), which requires that the size of the crystal needed by the α -BBO crystal is larger, but the transmission range of the YVO4 crystal can only reach about 400nm, which limits the application range of the crystal in a larger field.
According to the current development of inorganic birefringent crystal materials, the novel birefringent crystal is required to have not only a large birefringence, but also good comprehensive performance parameters, and is easy to generate a high-quality large-size bulk crystal, which requires extensive research work on a large number of systems. The search for high-performance birefringent crystal materials is one of the important issues in the field of optoelectronic functional materials, and people are continuously searching for birefringent crystals with better performance.
Patent application No. CN201910921550.X application of tin boron oxygen chlorine birefringent crystal, and the compound of patent application No. CN201910166628.1, namely tin boron oxygen chlorine and tin boron oxygen chlorine nonlinear optical crystal, and the preparation method and application thereof are earlier works of the applicant, and compared with the compound of tin boron oxygen bromine and tin boron oxygen bromine birefringent crystal, the preparation method and the application thereof, although the molecular formulas are similar, the crystal systems and space groups are the same, the crystal structures, the preparation growth processes, the optical properties and the application aspects of the crystal structures, the preparation growth processes, the optical properties and the application 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 the birefringence properties 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. Birefringent optical properties: bis of tin boron oxy bromide measured under the same conditions of 546nmThe refractive index is 0.439 and the tin boron oxy chlorine is 0.168 and is only one third of the tin boron oxy bromine, the fundamental reason for this performance gain is due to the effect of Br, which further illustrates that the two are similar in molecular formula but are not simple alternatives, since the introduction of Br allows a performance spanning flight. Birefringence field of application: the birefringence of the tin-boron-oxygen-bromine is larger, so that the birefringence value of all borate reported at present is exceeded, and the comprehensive performance of the tin-boron-oxygen-bromine complex also exceeds YVO widely used at present4Therefore, the device has wider application range and larger application potential after being cut into devices.
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 birefringent crystal of the formula 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 birefringent 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 birefringent crystal.
The chemical formula of the compound of the invention is tin boron oxygen bromineSn2B5O9Br 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 Sn-B-O-Br birefringent crystal with chemical formula 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 birefringent 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 birefringent 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 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 stopped2B5O9A Br birefringent crystal;
or growing crystals in a compound melt by using a kyropoulos method: fixing the seed crystal obtained in the step c on a seed crystal rod, placing the seed crystal in vacuum or inert atmosphere, and placing the seed crystal at the position of 0 DEG above the melt prepared in the step bCooling at the rate of 1-10 ℃/h to grow the crystal for 5-15 hours, slowly lifting the crystal, but continuing to grow without departing from the liquid level, repeating the steps, and obtaining the Sn-B-O-Br Sn after the crystal growth is stopped2B5O9A Br birefringent 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 Sn2B5O9A Br birefringent crystal;
the specific operation of growing the tin-boron-oxygen-bromine birefringent 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: mixing the mixture obtained in step bPlacing the melt in a single crystal furnace, placing the single crystal furnace in vacuum or inert atmosphere, slowly reducing the temperature to 400 ℃ at the speed of 0.1-2 ℃/h, and then rapidly reducing the temperature 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 stops2B5O9A Br birefringent crystal;
the specific operation of growing the tin-boron-oxygen-bromine birefringent 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 birefringent crystal, wherein the flux is SnBr2，H3BO3Or B2O3；
The specific operation of growing the tin-boron-oxygen-bromine birefringent crystal by the hydrothermal method is carried out according to the following steps:
a. the Sn-containing compound, the B-containing compound and the Br-containing compound are mixed according to the molar ratio of Sn to BBr 2: 5: 1, loading into platinum crucible, placing in muffle furnace, keeping constant temperature for 24-120 h at 300 deg.C under vacuum or inert atmosphere to obtain 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 Sn2B5O9A Br birefringent crystal;
the room temperature solution method is used for growing Sn-B-O-Br Sn2B5O9The specific operation of the Br birefringent 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 a2B5O9Placing Br polycrystalline powder into a cleaned glass container, adding 20100mL of deionized water, sonicated to dissolve the mixture well, 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 Sn2B5O9A Br birefringent crystal.
The tin-boron-oxygen-bromine birefringent crystal is used for preparing an optical isolator, a circulator, a beam shifter, an optical polarizer or an optical modulator.
The optical polarizer is a polarization beam splitter prism.
The polarization beam splitter prism is a Glan prism, a Wollaston prism or a Rochon prism.
The tin-boron-oxygen-bromine birefringent crystal is used in infrared-visible-ultraviolet bands, is a biaxial crystal, has a transmission range of 330-3500 nm and a birefringence of 0.244(3500nm) -0.293 (330 nm).
The invention relates to Sn-B-O-Br Sn2B5O9Br birefringent crystal of the formula Sn2B5O9Br with molecular weight of 515.37, and is prepared by solid phase synthesis or vacuum packaging; the chemical formula of the crystal is Sn2B5O9Br, molecular weight of 515.37, belonging to orthorhombic system, space group of Pnn2, unit cell parameter of Unit cell volume ofThe light transmission range is 330-3500 nm, and the birefringence is between 0.244(3500nm) -0.293 (330 nm). The crystal is easy to grow, easy to cut, easy to grind, easy to polish and easy to store. The method can be used for manufacturing polarization beam splitting prisms such as a Glan prism, a Wollaston prism, a Rochon prism or a beam splitting polarizer, and has important application in the fields of optics and communication.
Drawings
FIG. 1 is a powder XRD plot of the present invention;
FIG. 2 is a crystal structure of the present invention;
FIG. 3 is a graph of birefringence calculations according to the present invention;
FIG. 4 is a schematic diagram of a Glan prism of the present invention for use in the IR-visible-UV range;
FIG. 5 is a schematic diagram of a Wollaston prism for the IR-visible-UV band in accordance with the present invention;
FIG. 6 is a schematic diagram of a wedge-shaped birefringent crystal polarizing beam splitter of the present invention for use in the IR-visible-UV band;
FIG. 7 is a schematic diagram of an optical isolator for use in the IR-visible-UV range of the present invention, where a is the incoming light pass pattern and b is the reflected light block pattern.
Detailed Description
The invention is described in detail below with reference to the following figures and examples:
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