CN113638045A - Compound tin phosphate iodide and tin phosphate iodide birefringent crystal, and preparation method and application thereof - Google Patents

Compound tin phosphate iodide and tin phosphate iodide birefringent crystal, and preparation method and application thereof Download PDF

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CN113638045A
CN113638045A CN202110917055.9A CN202110917055A CN113638045A CN 113638045 A CN113638045 A CN 113638045A CN 202110917055 A CN202110917055 A CN 202110917055A CN 113638045 A CN113638045 A CN 113638045A
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CN113638045B (en
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潘世烈
郭靖宇
韩树娟
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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    • C30B9/00—Single-crystal growth from melt solutions using molten solvents
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/04—Prisms

Abstract

The invention provides a compound of tin phosphate iodide and tin phosphate iodide birefringent crystal, a preparation method and application thereof, wherein the chemical formula of the compound is Sn2PO4I, molecular weight of 459.25, is prepared by a solid phase reaction method or a vacuum packaging method, and the chemical formula of the crystal is Sn2PO4I, molecular weight of 459.25, belonging to orthorhombic system, space group ofCmcmCell parameter ofa=5.224(2)Å，b=8.069(3)Å，c=15.616(7)Å，α=90°，β=90°，γ=90 °, cell volume 658.2(5) A3The 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, the light transmission range is 380-3500nm, and the birefringence is between 0.432(3500nm) and 1.041(380 nm). The tin iodide phosphate birefringent crystal has moderate mechanical hardness, and is easy to cut, polish, process and store; has larger birefringence; the method has important application in the fields of optics and communication, and can be used for manufacturing a polarization beam splitter prism, a phase delay device, an electro-optical modulation device and the like.

Description

Compound tin phosphate iodide and tin phosphate iodide birefringent crystal, and preparation method and application thereof
Technical Field
The invention provides a compound of tin phosphate iodide and tin phosphate iodide birefringent crystal, a preparation method and application thereof, in particular to a compound of which the molecular formula is Sn for infrared-visible-ultraviolet bands2PO4Use of a tin phosphate iodide birefringent crystal of formula I.
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 an optically inhomogeneous 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 two electric field vectors having vibration directions perpendicular to each other, different propagation speeds, and different refractive indices, which 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 predominantly TiO2Crystal, LiNbO3Crystal, YVO4Crystal, alpha-BaB2O4Crystals and MgF2Crystals, and the like. With MgF2For example, the transmission range is 110-8500nm, the crystal is a birefringent crystal applied to deep ultraviolet, but the birefringence of the crystal is too small to be used for manufacturing a Glan prism and can only be used for a Rochon prism, and the light velocity separation angle is small, the size of a device is large, and the use is inconvenient. YVO4The crystal is a double-refraction crystal prepared artificially and is due to YVO4The melting point is high, the pulling growth must be carried out by using an iridium crucible, and the growing atmosphere is a weak oxygen atmosphere, so that the valence change problem of yttrium element exists during the growth, the quality of the crystal is reduced, and the high-quality crystal is difficult to obtain. Several borate birefringent crystals have been reported in recent years: high temperature phase alpha-BaB2O4The transmission range of the crystal is 189-3500nm and the birefringence index is 0.120@546nm, but the crystal has phase transfer and is easy to crack in the crystal growth process, so that the yield and the utilization rate of the crystal are influenced.
With the development of society, the demand of human beings for birefringent crystals is increasing, and the quality requirement is higher, so that the discovery of new excellent birefringent optical crystal materials is still a problem to be solved.
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.
Disclosure of Invention
The invention aims to provide a compound tin phosphate iodide, wherein the chemical formula of the compound is Sn2PO4I, molecular weight 459.25, belonging to orthorhombic system, space group of Ccm, unit cell parameter
Figure BDA0003206008770000011
Figure BDA0003206008770000012
Alpha is 90 deg., beta is 90 deg., gamma is 90 deg., unit cell volume is
Figure BDA0003206008770000013
The preparation method adopts a solid-phase reaction method or a vacuum packaging method.
Another object of the present invention is to provide a tin phosphate iodide birefringent crystal having a chemical formula of Sn2PO4I, molecular weight 459.25. Belongs to the orthorhombic system, the space group is Ccm, the cell parameter is
Figure BDA0003206008770000014
b＝8.069(3)
Figure BDA0003206008770000021
Beta is 90 deg., gamma is 90 deg., unit cell volume is
Figure BDA0003206008770000022
Still another object of the present invention is to provide a method for preparing birefringent tin phosphate iodide crystals, wherein the crystals are grown by a melt method, a high-temperature melt method, a vacuum encapsulation method, a hydrothermal method or a room-temperature solution method.
Still another object of the present invention is to provide use of the tin phosphate iodide birefringent crystal.
The chemical formula of the compound tin phosphate iodide is Sn2PO4I, molecular weight 459.25, and is prepared by solid phase synthesis or vacuum packaging.
A method for preparing the compound tin phosphate iodide as claimed in claim 1, which comprises the following steps:
the solid phase synthesis method is used for preparing a compound of tin phosphate iodide:
uniformly mixing a Sn-containing compound, a P-containing compound and a I-containing compound according to the molar ratio of Sn to P to I to 2 to 1, putting the mixture into a platinum crucible, putting the platinum crucible into a single crystal growth furnace in vacuum or inert atmosphere,heating to 450-650 ℃, keeping the temperature for more than 12 hours to obtain the compound Sn2PO4The Sn-containing compound is SnO or SnI2(ii) a The P-containing compound is (NH)4)3PO4、(NH4)2HPO4Or NH4H2PO4(ii) a Containing I as compound SnI2；
The vacuum packaging method is used for preparing a compound of tin phosphate iodide:
uniformly mixing a Sn-containing compound, a P-containing compound and a I-containing compound according to the molar ratio of Sn to P to I to 2 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 420-620 ℃ at the rate of 3-5 ℃/h, and keeping the temperature for more than 12 hours to obtain the compound Sn2PO4The Sn-containing compound is SnO or SnI2(ii) a The P-containing compound is (NH)4)3PO4、(NH4)2HPO4Or NH4H2PO4(ii) a Containing I as compound SnI2。
A tin iodide phosphate birefringent crystal, the chemical formula of the crystal is Sn2PO4I, molecular weight 459.25, belonging to orthorhombic system, space group of Ccm, unit cell parameter
Figure BDA0003206008770000023
Alpha is 90 deg., beta is 90 deg., gamma is 90 deg., unit cell volume is
Figure BDA0003206008770000024
The preparation method of the tin iodide 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 melt method for growing the tin iodide birefringent crystal comprises the following specific operations:
a. uniformly mixing a Sn-containing compound, a P-containing compound and a I-containing compound according to the molar ratio of Sn to P to I to 2 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 420-620 ℃ at the speed of 3-5 ℃/h, and keeping the temperature for more than 12 hours to obtain the compound Sn2PO4The Sn-containing compound is SnO or SnI2(ii) a The P-containing compound is (NH)4)3PO4、(NH4)2HPO4Or NH4H2PO4(ii) a Containing I as compound SnI2；
b. The compound Sn prepared in the step a2PO4I, placing the mixture into a platinum crucible, placing the platinum crucible in a muffle furnace, heating the mixture to the temperature of 650-800 ℃ in vacuum or inert atmosphere, and keeping the temperature for 24-60 hours to obtain a mixed melt;
c. c, slowly cooling the mixed melt obtained in the step b to 400 ℃ at the speed of 0.05-1 ℃/h, and then cooling to room temperature at the speed of 3-5 ℃/h to obtain Sn2PO4I, 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, lowering the seed crystal from the upper part of the mixed melt prepared in the step b, applying crystal rotation of 1-10rpm through a crystal growth controller, pulling the seed crystal at the speed of 0.5-5 mm/day, and simultaneously cooling at the speed of 0.05-1 ℃/h until the crystal stops growing, thus obtaining Sn2PO4I birefringent crystal;
or growing crystals in a melt of the compound by kyropoulos: c, fixing the seed crystal obtained in the step c on a seed crystal rod, lowering the seed crystal from the upper part of the melt prepared in the step b, cooling at the speed of 0.05-5 ℃/h to ensure that the crystal grows for 10-30 hours, slowly lifting the crystal without deviating from the liquid level to continue growing, repeating the steps, and obtaining Sn after the crystal growth is stopped2PO4I birefringent crystal;
or growing crystals in a compound melt by the 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 a2PO4I is put into a crucible, then the platinum crucible is put into a quartz tube for sealing, the temperature of a growth furnace is raised to 650 plus 800 ℃, the temperature is kept constant for 24 to 60 hours, then the crucible is reduced at the speed of 0.5 to 5 mm/day, and simultaneously, the growth temperature is kept unchanged or at the fastest speed of 1 ℃/hThe temperature reduction rate is reduced to 400 ℃, and after the growth is finished, the temperature is rapidly reduced to the room temperature at the rate of 3-5 ℃/h, and the Sn is obtained2PO4I birefringent crystal;
the high-temperature liquid-phase method for growing the tin iodide phosphate birefringent crystal comprises the following specific operations:
a. uniformly mixing a Sn-containing compound, a P-containing compound and a I-containing compound according to the molar ratio of Sn to P to I to 2 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 420-620 ℃ at the rate of 3-5 ℃/h, and keeping the temperature for more than 12 hours to obtain the compound Sn2PO4The Sn-containing compound is SnO or SnI2(ii) a The P-containing compound is (NH)4)3PO4、(NH4)2HPO4、NH4H2PO4(ii) a Containing I as compound SnI2；
b. The compound Sn obtained in the step a2PO4I, uniformly mixing the polycrystalline powder and the cosolvent according to the molar ratio of 1: 0.3-3, then putting the mixture into a platinum crucible, heating to 550-; the cosolvent is H3BO3、B2O3；
c. Preparing seed crystals: c, placing the mixed melt obtained in the step b into a single crystal furnace, slowly cooling to 550 ℃ at the speed of 0.05-1 ℃/h, and rapidly cooling to room temperature at the speed of 3-5 ℃/h to obtain Sn2PO4I, seed crystal;
d. growing a crystal: fixing the seed crystal obtained in the step c on a seed crystal rod, feeding the seed crystal from the upper part of the mixed melt prepared in the step b, applying crystal rotation of 1-10rpm through a crystal growth controller, cooling at the speed of 0.05-1 ℃/h, and obtaining Sn after crystal growth is stopped2PO4I birefringent crystal;
the vacuum packaging method for growing the tin iodide birefringent crystal comprises the following specific operations:
a. uniformly mixing a Sn-containing compound, a P-containing compound and an I-containing compound according to the molar ratio of Sn to P to I to 2 to 1Putting into a quartz tube, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, heating to 420-620 ℃ at the speed of 3-5 ℃/h, and keeping the temperature for more than 12 hours to obtain the compound Sn2PO4The Sn-containing compound is SnO or SnI2(ii) a The P-containing compound is (NH)4)3PO4、(NH4)2HPO4Or NH4H2PO4(ii) a Containing I as compound SnI2；
b. The compound Sn obtained in the step a2PO4I and cosolvent are evenly mixed according to the mol ratio of 0-1: 0.3-3, the mixture is put into a quartz tube, the quartz tube is placed into a muffle furnace after high-temperature sealing, the temperature is raised to 550-850 ℃, the temperature is kept for 12-60 hours, then the temperature is lowered to 450 ℃ at the speed of 0.05-1 ℃/h, and the temperature is rapidly lowered to the room temperature at the speed of 3-5 ℃/h, thus obtaining the Sn2PO4I birefringent crystal, and the cosolvent is H3BO3、B2O3；
The specific operation of growing the tin iodide phosphate birefringent crystal by the hydrothermal method is carried out according to the following steps:
a. uniformly mixing a Sn-containing compound, a P-containing compound and a I-containing compound according to the molar ratio of Sn to P to I to 2 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 420-620 ℃ at the rate of 3-5 ℃/h, and keeping the temperature for more than 12 hours to obtain the compound Sn2PO4The Sn-containing compound is SnO or SnI2(ii) a The P-containing compound is (NH)4)3PO4、(NH4)2HPO4Or NH4H2PO4(ii) a Containing I as compound SnI2；
b. The compound Sn obtained in the step a2PO4Dissolving in deionized water, ultrasonic treating at 50 deg.C, mixing completely, dissolving in HI and NH3·H2Adjusting the pH value to 6-12 by O to obtain a mixed solution;
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 50mL, and screwing and sealing the reaction kettle;
d. placing the high-pressure reaction kettle in a constant temperature box, heating to 120-320 ℃, keeping the temperature for 4-10 days, and then cooling to room temperature at the cooling rate of 2-10 ℃/day to obtain Sn2PO4I birefringent crystal;
the room temperature solution method for growing the tin iodide birefringent crystal comprises the following specific operations:
a. uniformly mixing a Sn-containing compound, a P-containing compound and a I-containing compound according to the molar ratio of Sn to P to I to 2 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 420-620 ℃ at the speed of 3-5 ℃/h, and keeping the temperature for more than 12 hours to obtain the compound Sn2PO4The Sn-containing compound is SnO or SnI2(ii) a The P-containing compound is (NH)4)3PO4、(NH4)2HPO4Or NH4H2PO4(ii) a Containing I as compound SnI2；
b. The compound Sn obtained in the step a2PO4I is put into a clean glass container, 10 to 50mL of deionized water is added, ultrasonic treatment is carried out to ensure that the mixture is fully mixed and dissolved, HI and NH are used3·H2Adjusting the pH value to 6-12 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 10 to 25 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 Sn2PO4I birefringent crystal.
The tin phosphate iodide Sn2PO4Use of an I birefringent crystal in the manufacture of an optical isolator, circulator, beam displacer, optical polariser or 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 compound of the invention, namely the tin iodide phosphate and the tin iodide phosphate birefringent crystal, as well as the preparation method and the application thereof, in the preparation of tin iodide phosphate Sn2PO4The container used in the preparation process of the I birefringent crystal is a platinum crucible, an iridium crucible, a ceramic crucible, a quartz tube, a conical flask and a beaker, and the inner lining is a polytetrafluoroethylene inner lining or a stainless steel inner lining hydrothermal kettle provided with a platinum sleeve. 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.
The compound tin phosphate iodide and tin phosphate iodide birefringent crystal, the preparation method and the application thereof are used for preparing tin phosphate iodide Sn2PO4The resistance furnace used in the preparation process of the I birefringent crystal is a muffle furnace or a drying oven.
The tin iodide birefringent crystal is used in infrared-visible-ultraviolet bands, is a biaxial crystal, has a transmittance range of 380-3500nm and a birefringence of 0.432(3500nm) -1.041(380 nm).
The tin phosphate iodide Sn of the invention2PO4I birefringent crystals, 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 XRD plot of the present invention;
FIG. 2 is a schematic diagram of the crystal structure of the present invention;
FIG. 3 is a calculated graph of birefringence according to the present invention;
FIG. 4 is a schematic view of a Glan prism for the infrared-visible-ultraviolet band made from the crystal obtained in the present invention;
FIG. 5 is a schematic view of a Wollaston prism for infrared-visible-ultraviolet bands made from the crystal obtained in the present invention;
FIG. 6 is a schematic view of a wedge-shaped birefringent crystal polarizing beam splitter for the infrared-visible-ultraviolet band made from the crystal obtained in the present invention, where 1 is the incident light; 2 is o light; 3 is e light; 4 is an optical axis; 5 is a crystal;
FIG. 7 is a schematic view of an optical isolator for infrared-visible-ultraviolet band fabricated using the crystal obtained by the present invention.
Detailed Description
The invention is described in detail below with reference to the following figures and examples:
example 1
Preparation of the compound:
according to the reaction formula: 3SnO + SnI2+2(NH4)3PO4→2Sn2PO4I+6NH3+3H2O, synthesizing compound Sn by adopting a solid-phase reaction method2PO4I：
SnO, SnI2、(NH4)3PO4Uniformly mixing the raw materials according to a molar ratio of 3:1:2, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 550 ℃ in vacuum or inert atmosphere, and keeping the temperature for 120 hours to obtain a compound Sn2PO4The polycrystalline powder of I.
Example 2
Preparation of the compound:
according to the reaction formula: 3SnO + SnI2+2(NH4)2HPO4→2Sn2PO4I+4NH3+3H2O, synthesizing compound Sn by adopting a solid-phase reaction method2PO4I：
SnO, SnI2、(NH4)2HPO4Uniformly mixing the components according to a molar ratio of 3:1:2, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, and heating the mixture to a temperature of 3:1:2 in vacuum or inert atmosphereKeeping the temperature at 550 ℃ for 120 hours to obtain a compound Sn2PO4The polycrystalline powder of I.
Example 3
Preparation of the compound:
according to the reaction formula: 3SnO + SnI2+2NH4H2PO4→2Sn2PO4I+2NH3+3H2O, synthesizing compound Sn by adopting a solid-phase reaction method2PO4I：
SnO, SnI2、NH4H2PO4Uniformly mixing the raw materials according to a molar ratio of 3:1:2, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 550 ℃ in vacuum or inert atmosphere, and keeping the temperature for 120 hours to obtain a compound Sn2PO4The polycrystalline powder of I.
Example 4
Preparation of the compound:
according to the reaction formula: 3SnO + SnI2+2(NH4)3PO4→2Sn2PO4I+6NH3+3H2O, synthesizing a compound Sn by adopting a vacuum packaging method2PO4I：
SnO, SnI2、NH4H2PO4Mixing uniformly according to a molar ratio of 2:1:1, placing into a quartz tube, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, heating to 420 ℃ at the speed of 3 ℃/h, and keeping the temperature for more than 12 hours to obtain the compound Sn2PO4I。
Example 5
According to the reaction formula: 3SnO + SnI2+2(NH4)2HPO4→2Sn2PO4I+4NH3+3H2O, synthesizing a compound Sn by adopting an empty encapsulation method2PO4I：
SnO, SnI2、(NH4)2HPO4Mixing uniformly according to a molar ratio of 2:1:1, placing into a quartz tube, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, and heating to 500 deg.C at a rate of 5 deg.C/hKeeping the temperature constant for 12 hours to obtain a compound Sn2PO4I。
Example 6
According to the reaction formula: 3SnO + SnI2+2NH4H2PO4→2Sn2PO4I+2NH3+3H2O, synthesizing a compound Sn by adopting a vacuum packaging method2PO4I：
SnO, SnI2、NH4H2PO4Mixing uniformly according to a molar ratio of 2:1:1, placing into a quartz tube, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, heating to 620 ℃ at the rate of 4 ℃/h, and keeping the temperature for more than 12 hours to obtain the compound Sn2PO4I。
Example 7
Growth of tin phosphate iodide Sn by melt method2PO4I birefringent crystal:
compound Sn obtained according to example 12PO4Putting the polycrystalline powder I into a platinum crucible, placing the platinum crucible in a muffle furnace, heating to 750 ℃ in vacuum, and keeping the temperature for 30 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 400 ℃ at the speed of 0.05 ℃/h, and rapidly cooling to room temperature at the speed of 3 ℃/h to obtain Sn2PO4I, seed crystal;
adopting a pulling method to grow crystals: fixing the obtained seed crystal on a seed crystal rod, discharging the seed crystal from the upper part of the mixed melt containing the prepared mixed melt, applying crystal rotation at 1rpm through a crystal growth controller, pulling the seed crystal at the speed of 0.5 mm/day, cooling at the speed of 0.05 ℃/h, and obtaining Sn with the size of 11mm multiplied by 8mm multiplied by 2mm after the crystal growth stops2PO4I birefringent crystal.
Example 8
Growth of tin phosphate iodide Sn by melt method2PO4I birefringent crystal:
the compound Sn obtained in example 22PO4I, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 650 ℃ under inert atmosphere, and keeping the temperature for 24 hoursObtaining a mixed melt;
slowly cooling the obtained mixed melt to 400 ℃ at the speed of 0.1 ℃/h, and then cooling to room temperature at the speed of 5 ℃/h to obtain Sn2PO4I, seed crystal;
adopting a pulling method to grow crystals in a compound melt: fixing the obtained seed crystal on a seed crystal rod, dropping the seed crystal from the upper part of the prepared mixed melt, applying crystal rotation of 5rpm through a crystal growth controller, pulling the seed crystal at the speed of 1 mm/day, and simultaneously cooling at the speed of 0.1 ℃/h until the crystal stops growing, thus obtaining Sn with the size of 8mm multiplied by 5mm multiplied by 1mm2PO4I birefringent crystal.
Example 9
Growth of tin phosphate iodide Sn by melt method2PO4I birefringent crystal:
the compound Sn obtained in example 32PO4I, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 700 ℃ in an inert atmosphere, and keeping the temperature for 60 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 400 ℃ at the speed of 0.5 ℃/h, and then cooling to room temperature at the speed of 3 ℃/h to obtain Sn2PO4I, seed crystal;
adopting a pulling method to grow crystals in a compound melt: fixing the obtained seed crystal on a seed crystal rod, dropping the seed crystal from the upper part of the prepared mixed melt, applying crystal rotation of 10rpm through a crystal growth controller, pulling the seed crystal at the speed of 5 mm/day, and simultaneously cooling at the speed of 1 ℃/h until the crystal stops growing, namely obtaining Sn with the size of 6mm multiplied by 5mm multiplied by 2mm2PO4I birefringent crystal;
adopting a pulling method to grow crystals in a compound melt: fixing the obtained seed crystal on a seed crystal rod, dropping the seed crystal from the upper part of the prepared mixed melt, applying crystal rotation of 5rpm through a crystal growth controller, pulling the seed crystal at the speed of 1 mm/day, simultaneously cooling at the speed of 0.1 ℃/h until the crystal stops growing, and obtaining Sn with the size of 10mm multiplied by 7mm multiplied by 2mm2PO4I birefringent crystal.
Example 10
Melt method for growing iodineChemical tin phosphate Sn2PO4I birefringent crystal:
the compound Sn prepared in example 42PO4I, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 680 ℃ in vacuum or inert atmosphere, and keeping the temperature for 40 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 400 ℃ at the speed of 1 ℃/h, and then cooling to room temperature at the speed of 4 ℃/h to obtain Sn2PO4I, seed crystal;
adopting a pulling method to grow crystals in a compound melt: fixing the obtained seed crystal on a seed crystal rod, dropping the seed crystal from the upper part of the prepared mixed melt, applying crystal rotation of 5rpm through a crystal growth controller, pulling the seed crystal at the speed of 5 mm/day, and simultaneously cooling at the speed of 0.5 ℃/h until the crystal stops growing, namely obtaining Sn with the size of 7mm multiplied by 4mm multiplied by 1mm2PO4I birefringent crystal;
example 11
Growth of tin phosphate iodide Sn by melt method2PO4I birefringent crystal:
the compound Sn prepared in example 52PO4I, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 750 ℃ in vacuum, and keeping the temperature for 35 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 400 ℃ at the speed of 1 ℃/h, and then cooling to room temperature at the speed of 5 ℃/h to obtain Sn2PO4I, seed crystal;
adopting a pulling method to grow crystals in a compound melt: fixing the obtained seed crystal on a seed crystal rod, dropping the seed crystal from the upper part of the prepared mixed melt, applying crystal rotation of 2rpm through a crystal growth controller, pulling the seed crystal at the speed of 2 mm/day, and simultaneously cooling at the speed of 0.5 ℃/h until the crystal stops growing, namely obtaining Sn with the size of 5mm multiplied by 3mm multiplied by 0.5mm2PO4I birefringent crystal.
Example 12
Growth of tin phosphate iodide Sn by melt method2PO4I birefringent crystal:
the compound Sn prepared in example 62PO4I, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 780 ℃ in an inert atmosphere, and keeping the temperature for 50 hours to obtain a mixed melt;
c. slowly cooling the obtained mixed melt to 400 ℃ at the speed of 1 ℃/h, and then cooling to room temperature at the speed of 4 ℃/h to obtain Sn2PO4I, seed crystal;
adopting a pulling method to grow crystals in a compound melt: fixing the obtained seed crystal on a seed crystal rod, dropping the seed crystal from the upper part of the prepared mixed melt, applying crystal rotation of 10rpm through a crystal growth controller, pulling the seed crystal at the speed of 5 mm/day, and simultaneously cooling at the speed of 0.05 ℃/h until the crystal stops growing, namely obtaining Sn with the size of 3mm multiplied by 2mm multiplied by 0.5mm2PO4I birefringent crystal.
Example 13
Growth of tin phosphate iodide Sn by melt method2PO4I birefringent crystal:
the compound Sn prepared in example 12PO4I, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 650 ℃ in vacuum or inert atmosphere, and keeping the temperature for 60 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 400 ℃ at the speed of 0.05 ℃/h, and then cooling to room temperature at the speed of 5 ℃/h to obtain Sn2PO4I, seed crystal;
growing crystals by a kyropoulos method: fixing the obtained seed crystal on a seed crystal rod, lowering the seed crystal from the upper part of the seed crystal containing the prepared mixed melt, reducing the temperature at the speed of 0.05 ℃/h to ensure that the crystal grows for 30 hours, slowly lifting the crystal without departing from the liquid level, continuing to grow, repeating the steps for three times to obtain the Sn with the size of 12mm multiplied by 10mm multiplied by 1mm2PO4I birefringent crystal.
Example 14
Growth of tin phosphate iodide Sn by melt method2PO4I birefringent crystal:
the compound Sn prepared in example 22PO4I, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 680 ℃ under an inert atmosphere, and keeping the temperature for 24 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 400 ℃ at the speed of 0.1 ℃/h, and then cooling to room temperature at the speed of 3 ℃/h to obtain Sn2PO4I, seed crystal;
growing crystals in a compound melt using the kyropoulos method: fixing the obtained seed crystal on a seed crystal rod, lowering the seed crystal from the upper part of the prepared melt, cooling at the speed of 0.5 ℃/h to ensure that the crystal grows for 10 hours, slowly lifting the crystal but continuing to grow without departing from the liquid level, repeating the steps, and obtaining Sn with the size of 8mm multiplied by 7mm multiplied by 1mm after the crystal growth is stopped2PO4I birefringent crystal.
Example 15
Growth of tin phosphate iodide Sn by melt method2PO4I birefringent crystal:
the compound Sn prepared in example 32PO4I, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 700 ℃ in vacuum, and keeping the temperature for 36 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 400 ℃ at the speed of 0.5 ℃/h, and then cooling to room temperature at the speed of 4 ℃/h to obtain Sn2PO4I, seed crystal;
growing crystals in a compound melt using the kyropoulos method: c, fixing the seed crystal obtained in the step c on a seed crystal rod, lowering the seed crystal from the upper part of the prepared melt, cooling at the speed of 1 ℃/h to grow the crystal for 15 hours, slowly lifting the crystal without deviating from the liquid level to continue growing, repeating the steps, and obtaining Sn with the size of 10mm multiplied by 5mm multiplied by 2mm after the crystal growth is stopped2PO4I birefringent crystal.
Example 16
Growth of tin phosphate iodide Sn by melt method2PO4I birefringent crystal:
the compound Sn prepared in example 42PO4I, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 750 ℃ in an inert atmosphere, and keeping the temperature for 40 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 400 ℃ at the speed of 1 ℃/h, and then cooling to room temperature at the speed of 3 ℃/h to obtain Sn2PO4I, seed crystal;
growing crystals in a compound melt using the kyropoulos method: c, fixing the seed crystal obtained in the step c on a seed crystal rod, lowering the seed crystal from the upper part of the prepared melt, cooling at the speed of 2 ℃/h to ensure that the crystal grows for 20 hours, slowly lifting the crystal without deviating from the liquid level to continue growing, repeating the steps, and obtaining Sn with the size of 9mm multiplied by 7mm multiplied by 2mm after the crystal growth is stopped2PO4I birefringent crystal.
Example 17
Growth of tin phosphate iodide Sn by melt method2PO4I birefringent crystal:
the compound Sn prepared in example 52PO4I, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 800 ℃ in vacuum, and keeping the temperature for 50 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 400 ℃ at the speed of 0.08 ℃/h, and then cooling to room temperature at the speed of 5 ℃/h to obtain Sn2PO4I, seed crystal;
growing crystals in a compound melt using the kyropoulos method: fixing the obtained seed crystal on a seed crystal rod, lowering the seed crystal from the upper part of the prepared melt at the speed of 3 ℃/h, enabling the crystal to grow for 25 hours, slowly lifting the crystal without deviating from the liquid level to continue to grow, repeating the steps, and obtaining Sn with the size of 6mm multiplied by 2mm multiplied by 1mm after the crystal growth is stopped2PO4I birefringent crystal.
Example 18
Growth of tin phosphate iodide Sn by melt method2PO4I birefringent crystal:
the compound Sn prepared in example 62PO4I, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 800 ℃ in an inert atmosphere, and keeping the temperature for 60 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 400 ℃ at the speed of 1 ℃/h, and then cooling to room temperature at the speed of 5 ℃/h to obtain Sn2PO4I, seed crystal;
growing crystals in a compound melt using the kyropoulos method: the obtained seed crystal is fixed on a seed crystal rod,lowering seed crystal from the upper part of the prepared melt, cooling at the speed of-5 ℃/h to ensure that the crystal grows for 30 hours, slowly lifting the crystal without departing from the liquid level to continue to grow, repeating the steps, and obtaining Sn with the size of 6mm multiplied by 2mm multiplied by 0.5mm after the crystal growth is stopped2PO4I birefringent crystal.
Example 19
Growth of tin phosphate iodide Sn by melt method2PO4I birefringent crystal:
the compound Sn prepared in example 12PO4I, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 800 ℃ in an inert atmosphere, and keeping the temperature for 24 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 400 ℃ at the speed of 1 ℃/h, and then cooling to room temperature at the speed of 5 ℃/h to obtain Sn2PO4I, seed crystal;
growing crystals in a compound melt using the Bridgman method: placing the obtained seed crystal at the bottom of the crucible, and then adding the compound Sn prepared in the step 12PO4I, putting the polycrystalline powder into a crucible, sealing the platinum crucible, raising the temperature of a growth furnace to 750 ℃, keeping the temperature for 24 hours, adjusting the position of the crucible to slightly melt the seed crystal, then reducing the crucible at a speed of 0.5 mm/day, reducing the temperature to 400 ℃ at a speed of 1 ℃/h, and after the growth is finished, rapidly reducing the temperature to room temperature at a speed of 3 ℃/h to obtain the Sn with the size of 15mm multiplied by 13mm multiplied by 2mm, thus obtaining the Sn2PO4I birefringent crystal.
Example 20
Growth of tin phosphate iodide Sn by melt method2PO4I birefringent crystal:
the compound Sn prepared in example 22PO4I, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 650 ℃ in vacuum or inert atmosphere, and keeping the temperature for 24 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 400 ℃ at the speed of 0.05 ℃/h, and then cooling to room temperature at the speed of 3 ℃/h to obtain Sn2PO4I, seed crystal;
growing crystals in a compound melt using the Bridgman method: will prepareIs placed at the bottom of the crucible, and the compound Sn prepared in example 2 is added2PO4I, placing the crucible into a platinum crucible, then placing the platinum crucible into a quartz tube for sealing, raising the temperature of a growth furnace to 650 ℃, keeping the temperature for 32 hours, then reducing the crucible at a speed of 0.8 mm/day, simultaneously keeping the growth temperature unchanged, and after the growth is finished, rapidly reducing the temperature to room temperature at a speed of 3 ℃/h to obtain Sn with the size of 12mm multiplied by 10mm multiplied by 2mm, thus obtaining the Sn2PO4I birefringent crystal.
Example 21
Growth of tin phosphate iodide Sn by melt method2PO4I birefringent crystal:
the compound Sn prepared in example 32PO4I, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 700 ℃ in an inert atmosphere, and keeping the temperature for 48 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 400 ℃ at the speed of 0.5 ℃/h, and then cooling to room temperature at the speed of 3 ℃/h to obtain Sn2PO4I, seed crystal;
growing crystals in a compound melt using the Bridgman method: the prepared seed crystal was placed at the bottom of the crucible, and the compound Sn prepared in example 3 was added2PO4I, placing the crucible into a crucible, then placing the platinum crucible into a quartz tube for sealing, raising the temperature of a growth furnace to 700 ℃, keeping the temperature for 48 hours, then reducing the crucible at a speed of 0.8 mm/day, reducing the temperature to 400 ℃ at a fastest speed of 1 ℃/h, and after the growth is finished, rapidly reducing the temperature to room temperature at a speed of 5 ℃/h to obtain Sn with the size of 10mm multiplied by 8mm multiplied by 2mm2PO4I birefringent crystal.
Example 22
Growth of tin phosphate iodide Sn by melt method2PO4I birefringent crystal:
the compound Sn prepared in example 42PO4I, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 800 ℃ in an inert atmosphere, and keeping the temperature for 60 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 400 ℃ at the speed of 1 ℃/h, and then cooling the mixed melt to the room at the speed of 4 ℃/hWarming to obtain Sn2PO4I, seed crystal;
growing crystals in a compound melt using the Bridgman method: the prepared seed crystal was placed at the bottom of the crucible, and the compound Sn prepared in example 4 was added2PO4I, placing the crucible into a platinum crucible, then placing the platinum crucible into a quartz tube for sealing, raising the temperature of a growth furnace to 800 ℃, keeping the temperature for 60 hours, then reducing the crucible at a speed of 2 mm/day, simultaneously keeping the growth temperature unchanged, and after the growth is finished, rapidly reducing the temperature to room temperature at a speed of 5 ℃/h to obtain Sn with the size of 10mm multiplied by 5mm multiplied by 2mm, thus obtaining the Sn2PO4I birefringent crystal.
Example 23
Growth of tin phosphate iodide Sn by melt method2PO4I birefringent crystal:
the compound Sn prepared in example 52PO4I, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 780 ℃ in vacuum, and keeping the temperature for 50 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 400 ℃ at the speed of 0.08 ℃/h, and then cooling to room temperature at the speed of 5 ℃/h to obtain Sn2PO4I, seed crystal;
growing crystals in a compound melt using the Bridgman method: the prepared seed crystal was placed at the bottom of the crucible, and the compound Sn prepared in example 5 was added2PO4I, placing the crucible into a platinum crucible, then placing the platinum crucible into a quartz tube for sealing, raising the temperature of a growth furnace to 780 ℃, keeping the temperature constant for 50 hours, then reducing the crucible at the speed of 2 mm/day, simultaneously keeping the growth temperature constant, and after the growth is finished, rapidly reducing the temperature to room temperature at the speed of 5 ℃/h to obtain Sn with the size of 8mm multiplied by 5mm multiplied by 1mm, thus obtaining the Sn2PO4I birefringent crystal.
Example 24
Growth of tin phosphate iodide Sn by melt method2PO4I birefringent crystal:
the compound Sn prepared in example 62PO4I, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to 680 ℃ under an inert atmosphere, and keeping the temperature for 36 hours to obtain a mixed melt;
slowly cooling the obtained mixed melt to 400 ℃ at the speed of 1 ℃/h, and then cooling to room temperature at the speed of 3 ℃/h to obtain Sn2PO4I, seed crystal;
growing crystals in a compound melt using the Bridgman method: the prepared seed crystal was placed at the bottom of the crucible, and the compound Sn prepared in example 6 was added2PO4I, placing the crucible into a crucible, then placing the platinum crucible into a quartz tube for sealing, raising the temperature of a growth furnace to 720 ℃, keeping the temperature for 58 hours, then reducing the crucible at a speed of 5 mm/day, reducing the temperature to 400 ℃ at a fastest speed of 1 ℃/h, and after the growth is finished, rapidly reducing the temperature to room temperature at a speed of 3 ℃/h to obtain Sn with the size of 6mm multiplied by 5mm multiplied by 1mm, thus obtaining the Sn2PO4I birefringent crystal.
Example 25
High-temperature melt method for growing tin (Sn) iodide phosphate2PO4I birefringent crystal:
compound Sn prepared as in example 12PO4I and a cosolvent B2O3Uniformly mixing the components according to the molar ratio of 1:1, putting the mixture into a platinum crucible, heating the mixture to 750 ℃, and keeping the temperature for 24 hours to obtain a mixed solution;
preparing seed crystals: placing the obtained mixed melt into a single crystal furnace, slowly cooling to 550 ℃ at the speed of 0.05 ℃/h, and then rapidly cooling to room temperature at the speed of 3 ℃/h to obtain Sn2PO4I, seed crystal;
growing a crystal: fixing the obtained seed crystal on a seed crystal rod, dropping the seed crystal from the upper part of the seed crystal containing the prepared mixed melt, applying crystal rotation at 1rpm through a crystal growth controller, cooling at the speed of 0.05 ℃/h, and obtaining the tin iodide phosphate Sn with the size of 13mm multiplied by 11mm multiplied by 1mm after the crystal growth stops2PO4I birefringent crystal.
Example 26
Growing the tin iodide birefringent crystal by a high-temperature melt method:
the compound Sn obtained in example 22PO4I and a cosolvent H3BO3Mixing uniformly according to the mol ratio of 1: 0.3, and then placing the mixture into a platinum crucibleHeating to 550 ℃, and keeping the temperature for 12 hours to obtain a mixed solution;
preparing seed crystals: placing the obtained mixed melt into a single crystal furnace, slowly cooling to 550 ℃ at the speed of 0.5 ℃/h, and then rapidly cooling to room temperature at the speed of 4 ℃/h to obtain Sn2PO4I, seed crystal;
growing a crystal: fixing the obtained seed crystal on a seed crystal rod, dropping the seed crystal from the upper part of the prepared mixed melt, applying crystal rotation of 5rpm through a crystal growth controller, cooling at the speed of 0.5 ℃/h, and obtaining Sn with the size of 12mm multiplied by 10mm multiplied by 2mm after the crystal growth stops2PO4I birefringent crystal.
Example 27
Growing the tin iodide birefringent crystal by a high-temperature melt method:
the compound Sn obtained in example 32PO4I and a cosolvent B2O3Uniformly mixing the components according to the molar ratio of 1:2, putting the mixture into a platinum crucible, heating the mixture to 650 ℃, and keeping the temperature for 36 hours to obtain mixed melt;
preparing seed crystals: placing the obtained mixed melt into a single crystal furnace, slowly cooling to 550 ℃ at the speed of 1 ℃/h, and then rapidly cooling to room temperature at the speed of 5 ℃/h to obtain Sn2PO4I, seed crystal;
growing a crystal: fixing the obtained seed crystal on a seed crystal rod, feeding the seed crystal from the upper part of the prepared mixed melt, applying crystal rotation of 8rpm through a crystal growth controller, cooling at the speed of 1 ℃/h, and obtaining Sn with the size of 9mm multiplied by 8mm multiplied by 3mm after the crystal growth is stopped2PO4I birefringent crystal.
Example 28
Growing the tin iodide birefringent crystal by a high-temperature melt method:
the compound Sn obtained in example 42PO4I and a cosolvent H3BO3Uniformly mixing the components according to the molar ratio of 1: 3, then putting the mixture into a platinum crucible, heating the mixture to 850 ℃, and keeping the temperature for 48 hours to obtain a mixed solution;
preparing seed crystals: placing the obtained mixed melt into a single crystal furnace at the speed of 0.05 ℃/hThe temperature is slowly reduced to 550 ℃, and then the temperature is rapidly reduced to room temperature at the speed of 4 ℃/h to obtain Sn2PO4I, seed crystal;
growing a crystal: fixing the obtained seed crystal on a seed crystal rod, dropping the seed crystal from the upper part of the prepared mixed melt, applying crystal rotation of 10rpm through a crystal growth controller, cooling at the speed of 0.05 ℃/h, and obtaining Sn with the size of 8mm multiplied by 7mm multiplied by 3mm after the crystal growth stops2PO4I birefringent crystal.
Example 29
Growing the tin iodide birefringent crystal by a high-temperature melt method:
the compound Sn obtained in example 52PO4I and a cosolvent B2O3Uniformly mixing the components according to the mol ratio of 1: 0.5, then putting the mixture into a platinum crucible, heating the mixture to 580 ℃, and keeping the temperature for 50 hours to obtain mixed melt;
preparing seed crystals: placing the obtained mixed melt into a single crystal furnace, slowly cooling to 550 ℃ at the speed of 0.08 ℃/h, and then rapidly cooling to room temperature at the speed of 3 ℃/h to obtain Sn2PO4I, seed crystal;
growing a crystal: fixing the obtained seed crystal on a seed crystal rod, dropping the seed crystal from the upper part of the prepared mixed melt, applying crystal rotation of 2rpm through a crystal growth controller, cooling at the speed of 0.08 ℃/h, and obtaining Sn with the size of 6mm multiplied by 5mm multiplied by 1mm after the crystal growth stops2PO4I birefringent crystal.
Example 30
Growing the tin iodide birefringent crystal by a high-temperature melt method:
the compound Sn obtained in example 62PO4I and a cosolvent B2O3Uniformly mixing the components according to the molar ratio of 1:2, then putting the mixture into a platinum crucible, heating the mixture to 850 ℃, and keeping the temperature for 60 hours to obtain a mixed solution;
preparing seed crystals: placing the obtained mixed melt into a single crystal furnace, slowly cooling to 550 ℃ at the speed of 0.8 ℃/h, and then rapidly cooling to room temperature at the speed of 4 ℃/h to obtain Sn2PO4I, seed crystal;
growing a crystal:fixing the obtained seed crystal on a seed crystal rod, dropping the seed crystal from the upper part of the prepared mixed melt, applying crystal rotation at 4rpm through a crystal growth controller, cooling at the speed of 0.8 ℃/h, and obtaining Sn with the size of 7mm multiplied by 4mm multiplied by 1mm after the crystal growth stops2PO4I birefringent crystal.
Example 31
Growth of tin phosphate iodide Sn by vacuum packaging method2PO4I birefringent crystal:
compound Sn prepared as in example 12PO4I and a cosolvent B2O3Mixing uniformly according to a mol ratio of 1:1, placing into a quartz tube with a diameter of 40mm, vacuumizing the quartz tube until the vacuum degree reaches 1 × 10-3Pa, sealing at high temperature, placing in a muffle furnace, heating to 750 deg.C, holding at constant temperature for 60 hr, cooling to 450 deg.C at a rate of 0.05 deg.C/h, and rapidly cooling to room temperature at a rate of 3 deg.C/h to obtain tin (Sn) iodide phosphate with size of 8mm × 6mm × 1mm2PO4I birefringent crystal.
Example 32
Growing a tin iodide birefringent crystal by a vacuum packaging method:
the compound Sn obtained in example 22PO4I and a cosolvent H3BO3Uniformly mixing the components according to a molar ratio of 0-1: 0.3, putting the mixture into a quartz tube, sealing the quartz tube at high temperature, putting the quartz tube into a muffle furnace, heating the muffle furnace to 550 ℃, keeping the temperature for 12 hours, then cooling the temperature to 450 ℃ at a speed of 0.5 ℃/h, and then rapidly cooling the temperature to room temperature at a speed of 4 ℃/h to obtain the Sn with the size of 7mm multiplied by 4mm multiplied by 1mm2PO4I birefringent crystal.
Example 33
Growing a tin iodide birefringent crystal by a vacuum packaging method:
the compound Sn obtained in example 32PO4I and a cosolvent B2O3Uniformly mixing the raw materials according to the mol ratio of 1: 0.5, putting the mixture into a quartz tube, sealing the quartz tube at high temperature, putting the quartz tube into a muffle furnace, heating the muffle furnace to 600 ℃, keeping the temperature for 24 hours, then cooling the muffle furnace to 450 ℃ at the speed of 0.08 ℃/h, and then rapidly cooling the muffle furnace to room temperature at the speed of 5 ℃/h to obtain the quartz tube with the size of 6mm multiplied by 3mm multiplied by 1mmSn2PO4I birefringent crystal.
Example 34
Growing a tin iodide birefringent crystal by a vacuum packaging method:
the compound Sn obtained in example 42PO4I and a cosolvent H3BO is uniformly mixed according to the mol ratio of 1:1, the mixture is put into a quartz tube, the quartz tube is sealed at high temperature and then placed in a muffle furnace, the temperature is raised to 650 ℃, the temperature is kept for 36 hours, then the temperature is lowered to 450 ℃ at the speed of 0.8 ℃/h, and the temperature is rapidly lowered to room temperature at the speed of 4 ℃/h, and the Sn with the size of 5mm multiplied by 4mm multiplied by 0.5mm is obtained2PO4I birefringent crystal.
Example 35
Growing a tin iodide birefringent crystal by a vacuum packaging method:
the compound Sn obtained in example 52PO4I and a cosolvent B2O3Uniformly mixing the components according to the mol ratio of 1: 3, putting the mixture into a quartz tube, sealing the quartz tube at high temperature, putting the quartz tube into a muffle furnace, heating the quartz tube to 850 ℃, keeping the temperature for 50 hours, then cooling the quartz tube to 450 ℃ at the speed of 1 ℃/h, and then rapidly cooling the quartz tube to room temperature at the speed of 5 ℃/h to obtain the Sn with the size of 5mm multiplied by 3mm multiplied by 0.5mm2PO4I birefringent crystal.
Example 36
Growing a tin iodide birefringent crystal by a vacuum packaging method:
the compound Sn obtained in example 62PO4I and a cosolvent H3BO3Uniformly mixing the components according to the mol ratio of 1: 3, putting the mixture into a quartz tube, sealing the quartz tube at high temperature, putting the quartz tube into a muffle furnace, heating the quartz tube to 850 ℃, keeping the temperature for 60 hours, then cooling the quartz tube to 450 ℃ at the speed of 1 ℃/h, and then rapidly cooling the quartz tube to room temperature at the speed of 5 ℃/h to obtain the Sn with the size of 6mm multiplied by 3mm multiplied by 0.5mm2PO4I birefringent crystal.
Example 37
Growth of tin (Sn) phosphate iodide by hydrothermal method2PO4I birefringent crystal:
compound Sn prepared according to example 12PO4Dissolving in deionized water to obtain a solutionThe mixture is treated by ultrasonic wave at 50 ℃ to be fully mixed and dissolved; with HI and NH3·H2Adjusting the pH value to 8 to obtain a mixed solution;
transferring the obtained mixed solution into a clean and pollution-free lining of a high-pressure reaction kettle with the volume of 50mL, and screwing and sealing the reaction kettle;
placing the high-pressure reaction kettle in a constant temperature box, heating to 120 ℃, keeping the temperature for 10 days, and then cooling to room temperature at a cooling rate of 2 ℃/day; thus obtaining Sn with the size of 5mm multiplied by 3mm multiplied by 2mm2PO4I birefringent crystal.
Example 38
Growing tin iodide birefringent crystal by a hydrothermal method:
the compound Sn obtained in example 22PO4Dissolving in deionized water, ultrasonic treating at 50 deg.C, mixing completely, dissolving in HI and NH3·H2Adjusting the pH value to 6 by O to obtain a mixed solution;
transferring the obtained mixed solution into a clean and pollution-free lining of a high-pressure reaction kettle with the volume of 50mL, and screwing and sealing the reaction kettle;
placing the high-pressure reaction kettle in a constant temperature box, heating to 150 ℃, keeping the temperature for 4 days, and then cooling to room temperature at a cooling rate of 3 ℃/day to obtain Sn with the size of 6mm multiplied by 3mm multiplied by 2mm2PO4I birefringent crystal.
Example 39
Growing tin iodide birefringent crystal by a hydrothermal method:
the compound Sn obtained in example 32PO4Dissolving in deionized water, ultrasonic treating at 50 deg.C, mixing completely, dissolving in HI and NH3·H2Adjusting the pH value to 10 to obtain a mixed solution;
transferring the obtained mixed solution into a clean and pollution-free lining of a high-pressure reaction kettle with the volume of 50mL, and screwing and sealing the reaction kettle;
placing the high-pressure reaction kettle in a constant temperature box, heating to 200 DEG CKeeping the temperature for 5 days, and cooling to room temperature at a cooling rate of 5 ℃/day to obtain Sn with the size of 5mm multiplied by 4mm multiplied by 1mm2PO4I birefringent crystal.
Example 40
Growing tin iodide birefringent crystal by a hydrothermal method:
the compound Sn obtained in example 42PO4Dissolving in deionized water, ultrasonic treating at 50 deg.C, mixing completely, dissolving in HI and NH3·H2Adjusting the pH value to 12 by O to obtain a mixed solution;
transferring the obtained mixed solution into a clean and pollution-free lining of a high-pressure reaction kettle with the volume of 50mL, and screwing and sealing the reaction kettle;
placing the high-pressure reaction kettle in a constant temperature box, heating to 250 ℃, keeping the temperature for 8 days, and then cooling to room temperature at a cooling rate of 6 ℃/day to obtain Sn with the size of 4mm multiplied by 2mm multiplied by 1mm2PO4I birefringent crystal.
EXAMPLE 41
Growing tin iodide birefringent crystal by a hydrothermal method:
the compound Sn obtained in example 52PO4Dissolving in deionized water, ultrasonic treating at 50 deg.C, mixing completely, dissolving in HI and NH3·H2Adjusting the pH value to 11 by O to obtain a mixed solution;
transferring the obtained mixed solution into a clean and pollution-free lining of a high-pressure reaction kettle with the volume of 50mL, and screwing and sealing the reaction kettle;
placing the high-pressure reaction kettle in a constant temperature box, heating to 300 ℃, keeping the temperature for 10 days, and then cooling to room temperature at a cooling rate of 10 ℃/day to obtain Sn with the size of 3mm multiplied by 2mm multiplied by 0.5mm2PO4I birefringent crystal.
Example 42
Growing tin iodide birefringent crystal by a hydrothermal method:
the compound Sn obtained in example 62PO4I is put into deionized water to be dissolved,subjecting the incompletely dissolved mixture to ultrasonic treatment at 50 deg.C to thoroughly mix and dissolve, treating with HI and NH3·H2Adjusting the pH value to 7 by O to obtain a mixed solution;
transferring the obtained mixed solution into a clean and pollution-free lining of a high-pressure reaction kettle with the volume of 50mL, and screwing and sealing the reaction kettle;
placing the high-pressure reaction kettle in a constant temperature box, heating to 320 ℃, keeping the temperature for 10 days, and then cooling to room temperature at a cooling rate of 10 ℃/day to obtain Sn with the size of 3mm multiplied by 2mm multiplied by 0.5mm2PO4I birefringent crystal.
Example 43
Growth of tin phosphate iodide Sn by room temperature solution method2PO4I birefringent crystal:
compound Sn prepared according to example 12PO4I is put into a clean glass container, 10mL of deionized water is added, ultrasonic treatment is carried out to ensure that the mixture is fully mixed and dissolved, HI and NH are used3·H2Adjusting the pH value of the solution to 8 by using O, and filtering by using filter paper to obtain a mixed solution;
placing the obtained mixed solution into a clean triangular flask, sealing the triangular flask with weighing paper, placing the triangular flask in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the sealing to adjust the evaporation rate of water in the aqueous solution, and standing the sealed mixed solution at room temperature for 10 days;
growing crystal particles on the bottom of the container until the size of the crystal particles is not obviously changed any more, and obtaining seed crystals;
selecting seed crystal with good quality, suspending in the prepared mixed solution, standing at room temperature for 30 days to obtain Sn with the size of 10mm × 8mm × 2mm2PO4I birefringent crystal.
Example 44
Growing a tin iodide birefringent crystal by a room-temperature solution method:
the compound Sn obtained in example 22PO4I is put into a clean glass container, 20mL of deionized water is added, ultrasonic treatment is carried out to ensure that the materials are fully mixed and dissolved, HI and NH are used3·H2Adjusting the pH value to 6 by using O, and filtering by using filter paper to obtain a mixed solution;
placing the obtained mixed solution in a clean glass container, sealing the container with weighing paper, placing the container in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the sealing to adjust the evaporation rate of water in the water solution, and standing the container at room temperature for 12 days;
growing crystal particles on the bottom of the container until the size of the crystal particles is not obviously changed any more, and obtaining seed crystals;
b, selecting seed crystals with better quality, suspending the seed crystals in the mixed solution prepared in the step b, and standing and growing for 20 days at room temperature to obtain Sn with the size of 9mm multiplied by 6mm multiplied by 1mm2PO4I birefringent crystal.
Example 45
Growing a tin iodide birefringent crystal by a room-temperature solution method:
the compound Sn obtained in example 32PO4I is put into a clean glass container, 30mL of deionized water is added, ultrasonic treatment is carried out to ensure that the materials are fully mixed and dissolved, HI and NH are used3·H2Adjusting the pH value to 10, and filtering with filter paper to obtain a mixed solution;
placing the obtained mixed solution in a clean glass container, sealing the container with weighing paper, placing the container in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the sealing to adjust the evaporation rate of water in the water solution, and standing the container for 15 days at room temperature;
growing crystal particles on the bottom of the container until the size of the crystal particles is not obviously changed any more, and obtaining seed crystals;
b, selecting seed crystals with better quality, suspending the seed crystals in the mixed solution prepared in the step b, and standing and growing for 25 days at room temperature to obtain Sn with the size of 6mm multiplied by 5mm multiplied by 1mm2PO4I birefringent crystal.
Example 46
Growing a tin iodide birefringent crystal by a room-temperature solution method:
the compound Sn obtained in example 42PO4I putting in cleaned glassIn a vessel, 40mL of deionized water was added, followed by sonication to mix well and dissolve, HI and NH3·H2Adjusting the pH value to 12, and filtering with filter paper to obtain a mixed solution;
placing the obtained mixed solution in a clean glass container, sealing the container with weighing paper, placing the container in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the sealing to adjust the evaporation rate of water in the water solution, and standing the container for 25 days at room temperature;
growing crystal particles on the bottom of the container until the size of the crystal particles is not obviously changed any more, and obtaining seed crystals;
b, selecting seed crystals with better quality, suspending the seed crystals in the mixed solution prepared in the step b, and standing and growing for 30 days at room temperature to obtain Sn with the size of 5mm multiplied by 3mm2PO4I birefringent crystal.
Example 47
Growing a tin iodide birefringent crystal by a room-temperature solution method:
the compound Sn obtained in example 52PO4I is put into a clean glass container, 50mL of deionized water is added, ultrasonic treatment is carried out to ensure that the materials are fully mixed and dissolved, HI and NH are used3·H2Adjusting the pH value to 11, and filtering with filter paper to obtain a mixed solution;
placing the obtained mixed solution in a clean glass container, sealing the container with weighing paper, placing the container in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the sealing to adjust the evaporation rate of water in the water solution, and standing the container for 18 days at room temperature;
growing crystal particles on the bottom of the container until the size of the crystal particles is not obviously changed any more, and obtaining seed crystals;
b, selecting seed crystals with better quality, suspending the seed crystals in the mixed solution prepared in the step b, standing and growing for 22 days at room temperature to obtain Sn with the size of 5mm multiplied by 3mm multiplied by 1mm2PO4I birefringent crystal.
Example 48
Growing a tin iodide birefringent crystal by a room-temperature solution method:
the compound Sn obtained in example 62PO4I is put into a clean glass container, 50mL of deionized water is added, ultrasonic treatment is carried out to ensure that the materials are fully mixed and dissolved, HI and NH are used3·H2Adjusting the pH value to 12, and filtering with filter paper to obtain a mixed solution;
placing the obtained mixed solution in a clean glass container, sealing the container with weighing paper, placing the container in a static environment without shaking, pollution and air convection, pricking a plurality of small holes on the sealing to adjust the evaporation rate of water in the water solution, and standing the container for 22 days at room temperature;
growing crystal particles on the bottom of the container until the size of the crystal particles is not obviously changed any more, and obtaining seed crystals;
b, selecting seed crystals with better quality, suspending the seed crystals in the mixed solution prepared in the step b, and standing and growing for 30 days at room temperature to obtain Sn with the size of 5mm multiplied by 2mm multiplied by 1mm2PO4I birefringent crystal.
Example 49
Sn phosphate iodide of any one of examples 7 to 482PO4I birefringent crystal glan prism:
processing the tin iodide phosphate birefringent crystal into two identical crystal prisms, wherein as shown in fig. 4, the light vertical incidence direction is along the crystallographic axis of the crystal, the incidence plane contains another two crystallographic axes, and the two prisms are connected together by an air thin layer along the inclined plane; or the connecting layer between the two prisms is changed into optical cement with different refractive indexes by air, so that the polarizing prism with different apex angle cutting is obtained, the design of 380-3400nm prism in a crystal light-transmitting wave band can be realized by adjusting the apex angle of the prism, when a beam of light is incident in a direction perpendicular to the incident surface, the light directions of the two beams of polarization directions which are mutually perpendicular do not deviate through the first prism of the Glan prism, and the incident angle on the inclined surface is equal to the included angle between the inclined surface and the right-angle surface of the prism (namely the apex angle of the prism). And selecting a proper vertex angle of the prism to enable one of the polarized lights to be totally reflected on the inclined plane, and emitting the other polarized light after passing through the connecting layers of the two prisms and the second prism.
Example 50
Sn phosphate iodide of any one of examples 7 to 482PO4I birefringent crystal manufacturing Wollaston prism:
two prisms are processed by a tin iodide birefringent crystal and then are bonded to form a Wollaston prism as shown in figure 5, the vertex angles of the two prisms are the same, but the incident surfaces and the emergent surfaces contain different crystallographic axes, the incident light vertically enters the end surface of the prism, two beams of polarized light with mutually perpendicular polarization directions in the first prism travel along the same direction at different speeds, when the light enters the second prism from the first prism, the refractive index changes because the crystallographic axes rotate 90 degrees along the incident direction, the two beams of linearly polarized light are separated due to birefringence respectively, the two separated polarized light are further separated due to secondary birefringence when entering air from the second prism, and the larger the birefringence of the crystal is, the more beneficial to the separation of the beams is.
Example 51
Sn phosphate iodide of any one of examples 7 to 482PO4I birefringent crystal manufacturing a polarization beam splitter:
tin iodide birefringent crystals are used for preparing a wedge-shaped birefringent crystal polarization beam splitter (as shown in figure 6), a wedge-shaped birefringent crystal 5 is provided, incident light 1 passes through the direction along the direction of the optical axis of the crystal, a beam of natural light enters along the direction of the optical axis of an optical main shaft and then can be divided into two beams of linearly polarized light (o light 2 and e light 3) through the crystal, the larger the birefringence, the farther the two beams of light can be separated, and the separation of the beams of light is facilitated.
Example 52
Sn phosphate iodide of any one of examples 7 to 482PO4I birefringent crystal manufacturing a polarization beam splitter:
tin iodide birefringent crystal was used to prepare an optical isolator, and a faraday rotator rotating the polarization plane of an incident beam by 45 ° was placed between a pair of birefringent crystal deflectors placed across from each other by 45 °, to construct an optical isolator which allows only a forward propagating beam to pass through the system, while blocking a backward propagating beam, fig. 7a shows that the incident beam can pass through, and fig. 7b shows that the reflected light is blocked.

Claims (7)

1. A compound of tin iodide phosphate, which is characterized in that the chemical formula of the compound is Sn2PO4I, molecular weight 459.25, and is prepared by solid phase synthesis or vacuum packaging.
2. A method for preparing the compound tin phosphate iodide as claimed in claim 1, which comprises the following steps:
the solid phase synthesis method is used for preparing a compound of tin phosphate iodide:
uniformly mixing a Sn-containing compound, a P-containing compound and a I-containing compound according to the molar ratio of Sn to P to I to 2 to 1, putting the mixture into a platinum crucible, putting the platinum crucible into a single crystal growth furnace, heating the mixture to 450 ℃ and 650 ℃ in a vacuum or inert atmosphere, and keeping the temperature for more than 12 hours to obtain the Sn-containing compound2PO4The Sn-containing compound is SnO or SnI2(ii) a The P-containing compound is (NH)4)3PO4、(NH4)2HPO4Or NH4H2PO4(ii) a Containing I as compound SnI2；
The vacuum packaging method is used for preparing a compound of tin phosphate iodide:
uniformly mixing a Sn-containing compound, a P-containing compound and a I-containing compound according to the molar ratio of Sn to P to I to 2 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 420-620 ℃ at the rate of 3-5 ℃/h, and keeping the temperature for more than 12 hours to obtain the compound Sn2PO4The Sn-containing compound is SnO or SnI2(ii) a The P-containing compound is (NH)4)3PO4、(NH4)2HPO4Or NH4H2PO4(ii) a Containing I as compound SnI2。
3. A tin iodide birefringent crystal is characterized in that the chemical formula of the crystal is Sn2PO4I, divide intoA quantum of 459.25, belongs to the orthorhombic system, and has a space group ofCmcmCell parameter ofa = 5.224(2) Å，b =8.069(3) Å，c = 15.616(7) Å，α= 90°，β= 90°，γ=90 °, cell volume 658.2(5) A3。
4. A process for producing a birefringent tin phosphate iodide crystal according to claim 3, wherein 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 melt method for growing the tin iodide birefringent crystal comprises the following specific operations:
a. uniformly mixing a Sn-containing compound, a P-containing compound and a I-containing compound according to the molar ratio of Sn to P to I to 2 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 420-620 ℃ at the speed of 3-5 ℃/h, and keeping the temperature for more than 12 hours to obtain the compound Sn2PO4The Sn-containing compound is SnO or SnI2(ii) a The P-containing compound is (NH)4)3PO4、(NH4)2HPO4Or NH4H2PO4(ii) a Containing I as compound SnI2；
b. The compound Sn prepared in the step a2PO4I, placing the mixture into a platinum crucible, placing the platinum crucible in a muffle furnace, heating the mixture to the temperature of 650-800 ℃ in vacuum or inert atmosphere, and keeping the temperature for 24-60 hours to obtain a mixed melt;
c. c, slowly cooling the mixed melt obtained in the step b to 400 ℃ at the speed of 0.05-1 ℃/h, and then cooling to room temperature at the speed of 3-5 ℃/h to obtain Sn2PO4I, 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, lowering the seed crystal from the upper part of the mixed melt prepared in the step b, applying crystal rotation of 1-10rpm through a crystal growth controller, pulling the seed crystal at the speed of 0.5-5 mm/day, and simultaneously cooling at the speed of 0.05-1 ℃/h until the crystal stops growing, thus obtaining Sn2PO4I birefringent crystal;
or growing crystals in a melt of the compound by kyropoulos: c, fixing the seed crystal obtained in the step c on a seed crystal rod, lowering the seed crystal from the upper part of the melt prepared in the step b, cooling at the speed of 0.05-5 ℃/h to ensure that the crystal grows for 10-30 hours, slowly lifting the crystal without deviating from the liquid level to continue growing, repeating the steps, and obtaining Sn after the crystal growth is stopped2PO4I birefringent crystal;
or growing crystals in a compound melt by the 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 a2PO4I is put into a crucible, then the platinum crucible is put into a quartz tube for sealing, the temperature of a growth furnace is raised to 650 plus materials 800 ℃, the temperature is kept for 24-60 hours, then the crucible is reduced at the speed of 0.5-5 mm/day, simultaneously, the growth temperature is kept unchanged, or the temperature is reduced to 400 ℃ at the fastest speed of 1 ℃/h, after the growth is finished, the temperature is rapidly reduced to the room temperature at the speed of 3-5 ℃/h, and then the Sn is obtained2PO4I birefringent crystal;
the high-temperature liquid-phase method for growing the tin iodide phosphate birefringent crystal comprises the following specific operations:
a. uniformly mixing a Sn-containing compound, a P-containing compound and a I-containing compound according to the molar ratio of Sn to P to I to 2 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 420-620 ℃ at the rate of 3-5 ℃/h, and keeping the temperature for more than 12 hours to obtain the compound Sn2PO4The Sn-containing compound is SnO or SnI2(ii) a The P-containing compound is (NH)4)3PO4、(NH4)2HPO4、NH4H2PO4(ii) a Containing I as compound SnI2；
b. The compound Sn obtained in the step a2PO4I, uniformly mixing the polycrystalline powder and the cosolvent according to the molar ratio of 1: 0.3-3, then putting the mixture into a platinum crucible, heating to 550-; the cosolvent is H3BO3、B2O3；
c. Preparing seed crystals: c, placing the mixed melt obtained in the step b into a single crystal furnace, slowly cooling to 550 ℃ at the speed of 0.05-1 ℃/h, and rapidly cooling to room temperature at the speed of 3-5 ℃/h to obtain Sn2PO4I, seed crystal;
d. growing a crystal: fixing the seed crystal obtained in the step c on a seed crystal rod, feeding the seed crystal from the upper part of the mixed melt prepared in the step b, applying crystal rotation of 1-10rpm through a crystal growth controller, cooling at the speed of 0.05-1 ℃/h, and obtaining Sn after crystal growth is stopped2PO4I birefringent crystal;
the vacuum packaging method for growing the tin iodide birefringent crystal comprises the following specific operations:
a. uniformly mixing a Sn-containing compound, a P-containing compound and a I-containing compound according to the molar ratio of Sn to P to I to 2 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 420-620 ℃ at the speed of 3-5 ℃/h, and keeping the temperature for more than 12 hours to obtain the compound Sn2PO4The Sn-containing compound is SnO or SnI2(ii) a The P-containing compound is (NH)4)3PO4、(NH4)2HPO4Or NH4H2PO4(ii) a Containing I as compound SnI2；
b. The compound Sn obtained in the step a2PO4I and cosolvent are evenly mixed according to the mol ratio of 1: 0.3-3, the mixture is put into a quartz tube, the quartz tube is placed in a muffle furnace after high-temperature sealing, the temperature is raised to 550-850 ℃, the temperature is kept for 12-60 hours, then the temperature is lowered to 450 ℃ at the speed of 0.05-1 ℃/h, and the temperature is rapidly lowered to the room temperature at the speed of 3-5 ℃/h, thus obtaining the Sn2PO4I birefringent crystal, and the cosolvent is H3BO3、B2O3；
The specific operation of growing the tin iodide phosphate birefringent crystal by the hydrothermal method is carried out according to the following steps:
a. uniformly mixing a Sn-containing compound, a P-containing compound and an I-containing compound according to the molar ratio of Sn to P to I to 2 to 1, filling the mixture into a quartz tube,the quartz tube is vacuumized, and the vacuum degree reaches 1 multiplied by 10−3Pa, sealing at high temperature, placing in a muffle furnace, heating to 420-620 ℃ at the rate of 3-5 ℃/h, and keeping the temperature for more than 12 hours to obtain the compound Sn2PO4The Sn-containing compound is SnO or SnI2(ii) a The P-containing compound is (NH)4)3PO4、(NH4)2HPO4Or NH4H2PO4(ii) a Containing I as compound SnI2；
b. The compound Sn obtained in the step a2PO4Dissolving in deionized water, ultrasonic treating at 50 deg.C, mixing completely, dissolving in HI and NH3·H2Adjusting the pH value to 6-12 by O to obtain a mixed solution;
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 50mL, and screwing and sealing the reaction kettle;
d. placing the high-pressure reaction kettle in a constant temperature box, heating to 120-320 ℃, keeping the temperature for 4-10 days, and then cooling to room temperature at the cooling rate of 2-10 ℃/day to obtain Sn2PO4I birefringent crystal;
the room temperature solution method for growing the tin iodide birefringent crystal comprises the following specific operations:
a. uniformly mixing a Sn-containing compound, a P-containing compound and a I-containing compound according to the molar ratio of Sn to P to I to 2 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 420-620 ℃ at the speed of 3-5 ℃/h, and keeping the temperature for more than 12 hours to obtain the compound Sn2PO4The Sn-containing compound is SnO or SnI2(ii) a The P-containing compound is (NH)4)3PO4、(NH4)2HPO4Or NH4H2PO4(ii) a Containing I as compound SnI2；
b. The compound Sn obtained in the step a2PO4I, putting the mixture into a cleaned glass container, adding 10-50mL of deionized water, and then ultrasonically treatingMixing thoroughly to dissolve, adding HI and NH3·H2Adjusting the pH value to 6-12 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 10 to 25 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 Sn2PO4I birefringent crystal.
5. Tin (ll) phosphate iodide Sn according to claim 32PO4Use of an I birefringent crystal in the manufacture of an optical isolator, circulator, beam displacer, optical polariser or optical modulator.
6. Use according to claim 5, characterized in that the optical polarizer is a polarizing beam splitter prism.
7. Use according to claim 6, characterized in that the polarizing beam splitting prism is a Glan prism, a Wollaston prism or a Rochon prism.
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Publication number Priority date Publication date Assignee Title
CN115386954A (en) * 2022-09-17 2022-11-25 中国科学院新疆理化技术研究所 Compound sodium lithium fluoroborate, lithium sodium fluoroborate birefringent crystal, preparation method and application
CN115385351A (en) * 2022-09-17 2022-11-25 中国科学院新疆理化技术研究所 Compound potassium lithium fluoborate, lithium potassium fluoborate birefringent crystal, preparation method and application
CN117490409A (en) * 2023-12-29 2024-02-02 河南梦瑶科技有限公司 Smelting device of high-phosphorus copper alloy
CN117490409B (en) * 2023-12-29 2024-03-22 河南梦瑶科技有限公司 Smelting device of high-phosphorus copper alloy

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