CN114956110B - Compound cesium trichloroborate and cesium trichloroborate birefringent crystal, and preparation method and application thereof - Google Patents
Compound cesium trichloroborate and cesium trichloroborate birefringent crystal, and preparation method and application thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 238
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- -1 Compound cesium trichloroborate Chemical class 0.000 title claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 59
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 51
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000000935 solvent evaporation Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 51
- 239000011521 glass Substances 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 238000000227 grinding Methods 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 27
- 238000005303 weighing Methods 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 230000003287 optical effect Effects 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000004570 mortar (masonry) Substances 0.000 claims description 18
- 238000007789 sealing Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- 238000002441 X-ray diffraction Methods 0.000 claims description 9
- 238000002083 X-ray spectrum Methods 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 230000001276 controlling effect Effects 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 9
- 239000004800 polyvinyl chloride Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000003755 preservative agent Substances 0.000 claims description 9
- 230000002335 preservative effect Effects 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 239000010431 corundum Substances 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 4
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 claims description 4
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001942 caesium oxide Inorganic materials 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 230000010287 polarization Effects 0.000 abstract description 4
- 238000004891 communication Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 description 69
- 239000000463 material Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- VTOPDGYETFJKQE-UHFFFAOYSA-N boric acid;cesium Chemical compound [Cs].OB(O)O VTOPDGYETFJKQE-UHFFFAOYSA-N 0.000 description 7
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- 229910021532 Calcite Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/121—Borates of alkali metal
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
- C30B7/04—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent using aqueous solvents
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/28—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for polarising
- G02B27/283—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for polarising used for beam splitting or combining
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/24—Coupling light guides
- G02B6/26—Optical coupling means
- G02B6/27—Optical coupling means with polarisation selective and adjusting means
- G02B6/2746—Optical coupling means with polarisation selective and adjusting means comprising non-reciprocal devices, e.g. isolators, FRM, circulators, quasi-isolators
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
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Abstract
The invention relates to a compound of cesium trichloroborate and cesium trichloroborate birefringent crystal, a preparation method and application thereof, wherein the molecular formula of the compound is CsB 3 O 3 (OH) 3 Cl, molecular weight 299.81, was prepared by mild solvent evaporation. The chemical formula of the crystal is CsB 3 O 3 (OH) 3 Cl with molecular weight of 299.81 belongs to monoclinic system, and space group isP2 1 /cUnit cell parameters a= 8.175 (3) a, b= 7.927 (2) a, c= 14.096 (4) a, β= 120.219 (17), v= 789.3 (4) a 3 Z=4, and the crystal was grown by room temperature solution method or hydrothermal method, and the ultraviolet transmission cut-off side of the crystal was 180nm, and the birefringence was about 0.109 (532 nm). The cesium trichloro-tri-borate birefringent crystal has moderate mechanical hardness, and is easy to grow, cut, polish, process and store; has larger double refractive index; 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
Technical Field
The invention relates to a compound of three hydroxyl chlorine cesium triborate and three hydroxyl chlorine cesium triborate birefringent crystal, a preparation method and application, in particular to a molecular formula CsB for visible light-deep ultraviolet band 3 O 3 (OH) 3 Trihydroxy of ClCesium chloride triborate birefringent crystals.
Background
Birefringence refers to the phenomenon whereby a beam of light impinges on a crystal surface to produce two beams of refracted light, the root cause of this phenomenon being the anisotropy of the crystal material. When light propagates through an optically non-homogeneous body (e.g., a crystal other than a cubic system), the vibration characteristics of the light are changed except for the specific directions (along the optical axis direction), and the light is decomposed into two polarized lights with two electric field vector vibration directions perpendicular to each other, different propagation speeds and different refractive indexes, and the phenomenon is called birefringence, and the crystal is called a birefringent crystal. The birefringence property of the crystal is an important optical performance parameter of the crystal of the photoelectric functional material, linear polarized light can be obtained by utilizing the characteristics of the birefringence crystal, and displacement of light beams and the like can be realized, so that the birefringence crystal becomes a key material for manufacturing optical elements such as an optical isolator, an circulator, a light beam shifter, an optical polarizer, an optical modulator and the like.
The common birefringent materials are mainly calcite crystal, rutile crystal and LiNbO 3 Crystal, YVO 4 Crystals, alpha-BaB 2 O 4 Crystal and MgF 2 Crystals, and the like. By MgF 2 For example, the transmission range is 110-8500nm, which is a crystal material with good application to deep ultraviolet, but the birefringence is too small, so that the crystal material is not suitable for manufacturing a gram prism, can only be used for a Rochon prism, has small light speed separation angle, large period size and inconvenient use; the double refractive index of the quartz crystal is also very small, and the same problem exists; YVO 4 The crystal is also an artificially prepared birefringent crystal and is due to YVO 4 The melting point is high, the iridium crucible is required to be used for carrying out pulling growth, and the growth atmosphere is a weak oxygen atmosphere, so that the problem of valence change of yttrium element exists during growth, the quality of the crystal is reduced, high-quality crystal is not easy to obtain, the transmission range of the crystal is 400-5000nm, and the crystal cannot be directly used in the ultraviolet region. Calcite in its natural form is a birefringent crystal which is widely used but has a high impurity content, and ordinary crystals can only use a wavelength band of 350nm or more, which makes it difficult to obtain ultraviolet light grade calcite crystals, which makesThe deep ultraviolet region can not be reached by using the wave band<250 nm). Rutile also exists mainly in a natural form, is difficult to synthesize artificially, has small size and large hardness, and is difficult to process. Several borate birefringent crystals have been reported in recent years: high temperature phase BaB 2 O 4 The transmission range of the crystal is 189-3500nm, the double refractive index is larger, but the crystal has phase transfer and is easy to crack in the crystal growth process, thereby influencing the yield and the utilization rate of the crystal.
With the development of society, the demand of human beings for birefringent crystals is increasing, and the quality requirement is increasing, so finding new and excellent birefringent optical crystal materials is still a problem to be solved.
According to the development of the current inorganic birefringent crystal material, the novel birefringent crystal is required to have large birefringent index, good comprehensive performance parameters and easy generation of high-quality large-size bulk crystal, and a great deal of systematic and intensive research work is required. The search for high-performance birefringent crystal materials is one of the important subjects in the field of optoelectronic functional materials, and the search for birefringent crystals with better performance is still ongoing.
Disclosure of Invention
The invention aims to provide a compound cesium trichloroperborate and a cesium trichloroperborate birefringent crystal, wherein the molecular formula of the compound is CsB 3 O 3 (OH) 3 Cl, molecular weight 299.81, was prepared by mild solvent evaporation. The molecular formula of the crystal is CsB 3 O 3 (OH) 3 Cl with molecular weight of 299.81 belongs to monoclinic system, and the space group is P2 1 Unit cell parameters/cβ＝120.219(17)， Z＝4。
The invention also aims to provide a preparation method of the compound cesium trichloroborate and the cesium trichloroborate birefringent crystal.
It is a further object of the present invention to provide the use of cesium trishydroxychlorotri-borate birefringent crystals.
The invention relates to a compound of cesium trichlorotriborate, which is characterized in that the molecular formula of the compound is CsB 3 O 3 (OH) 3 Cl, molecular weight 299.81, was prepared by mild solvent evaporation.
The preparation method of the compound cesium trichloroborate comprises the following steps:
weighing cesium-containing compound cesium chloride, cesium hydroxide, cesium oxide, cesium carbonate, cesium bicarbonate, cesium sulfate or cesium nitrate with purity of 99.9% and boron-containing compound boric acid or boron oxide with purity of 99.9% according to a molar ratio of Cs:B=1:3, putting into a mortar, adding 5-10mL of deionized water for careful grinding, then putting into a 100mL open glass beaker or corundum crucible, putting into a magnetic heating stirrer or a water bath kettle, slowly heating to 80-100 ℃, keeping the temperature for 1-5 hours, taking out after a sample is dried, fully grinding to obtain single-phase polycrystalline powder of the cesium trichlorotriborate compound, putting into the mortar for grinding for X-ray analysis, and obtaining an X-ray spectrogram and CsB 3 O 3 (OH) 3 The X-ray spectra obtained for the Cl single crystal structure are consistent.
Cesium trishydroxychlorotriborate birefringent crystal with molecular formula CsB 3 O 3 (OH) 3 Cl with molecular weight of 299.81 belongs to monoclinic system, and the space group is P2 1 Unit cell parameters/c β＝120.219(17)，/>Z＝4。
The preparation method of the cesium trichloro-tri-borate birefringent crystal adopts a room-temperature solution method or a hydrothermal method to grow the cesium trichloro-tri-borate birefringent crystal:
the room temperature solution method for growing the cesium tri-hydroxy-chloride-tri-borate birefringent crystal comprises the following steps:
a. weighing and putting a Cs-containing compound and a B-containing compound into a 1000mL glass flask according to a molar ratio of Cs to B=1 to 3, adding 500mL of deionized water, performing ultrasonic treatment for 5-60 minutes to fully mix and dissolve the Cs-containing compound and the B-containing compound, adding a hydrochloric acid solution with the concentration of 37%, adjusting the pH value of the solution to 1-7, sealing the solution by using a polyvinyl chloride film, sealing 20 small holes in the film for volatilizing a solvent in the solution, putting the glass flask into a water bath crystal growing device to obtain a mixed solution, wherein the Cs-containing compound is CsCl, csOH, cs 2 O、Cs 2 CO 3 、CsHCO 3 、Cs 2 SO 4 Or CsNO 3 The B-containing compound being H 3 BO 3 Or B is a 2 O 3 ；
b. Preparing seed crystals: c, keeping the mixed solution obtained in the step a at the constant temperature of 80-90 ℃ and waiting for the solvent to volatilize and spontaneously crystallizing to obtain seed crystals;
c. growing crystals in a solution of the compound: b, fixing the seed crystal obtained in the step b on a seed rod, putting the seed crystal into a glass flask in a water bath crystal raising device, immersing the seed crystal into the solution, keeping the constant temperature, controlling the evaporation rate of the solvent through the size and the number of small holes on the preservative film, and rotating the seed rod at a rotating speed of 0-100 rpm;
d. after the crystal grows to the required size, the crystal is lifted off the liquid level and cooled to room temperature at the speed of 1-10 ℃/h, and then the crystal is taken out of the water bath crystal-growing device, thus obtaining the CsB 3 O 3 (OH) 3 Cl birefringent crystal;
the preparation method of the cesium tri-hydroxy-chloride-tri-borate birefringent crystal by the hydrothermal method comprises the following steps:
a. weighing and uniformly mixing a Cs-containing compound and a B-containing compound according to a molar ratio Cs:B=1:3, putting the mixture into a clean and pollution-free hydrothermal kettle with a volume of 100mL, adding 5-25mL of deionized water until solute is dissolved, adding a hydrochloric acid solution with a concentration of 37%, and regulating the pH value of the solution to be 1-7;
b. the reaction kettle is tightly screwed and sealed, is put into a drying oven, is heated to 100-220 ℃ at the speed of 10-30 ℃/h, is kept at the constant temperature for 10-48 hours, is then cooled to 25 ℃ at the speed of 1-5 ℃/h, and is opened to obtain the CsB 3 O 3 (OH) 3 Cl crystals.
The application of the cesium trichloro-tri-borate birefringent crystal in 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 splitting prism is a gram prism, a Wollaston prism or a Rochon prism.
The preparation method of the compound cesium trichloroborate and cesium trichloroborate birefringent crystal adopts a mild solvent evaporation method to synthesize the compound, adopts a room temperature solution method or a hydrothermal method to grow the cesium trichloroborate birefringent crystal, and has the chemical reaction formula:
CsCl+3H 3 BO 3 ＝CsB 3 O 3 (OH) 3 Cl+3H 2 O；
CsOH+3H 3 BO 3 +HCl＝CsB 3 O 3 (OH) 3 Cl+4H 2 O；
Cs 2 O+6H 3 BO 3 +2HCl＝2CsB 3 O 3 (OH) 3 Cl+7H 2 O；
Cs 2 CO 3 +6H 3 BO 3 +2HCl＝2CsB 3 O 3 (OH) 3 Cl+7H 2 O+CO 2 ↑；
CsHCO 3 +3H 3 BO 3 +HCl＝CsB 3 O 3 (OH) 3 Cl+4H 2 O+CO 2 ↑；
Cs 2 SO 4 +6H 3 BO 3 +2HCl＝2CsB 3 O 3 (OH) 3 Cl+6H 2 O+H 2 SO 4 ；
CsNO 3 +3H 3 BO 3 +HCl＝CsB 3 O 3 (OH) 3 Cl+3H 2 O+HNO 3 。
the chemical formula of the tri-hydroxy cesium chlorotriborate birefringent crystal is CsB 3 O 3 (OH) 3 Cl with molecular weight of 299.81 belongs to monoclinic system, and the space group is P2 1 Unit cell parameters/c β＝120.219(17)，/>Z=4. The crystal is grown by a room temperature solution method or a hydrothermal method, and is used for a visible light-deep ultraviolet band, the ultraviolet transmission cut-off edge of the crystal is 180nm, and the double refraction index of the crystal is about 0.109 (532 nm). The crystal is easy to grow, cut, polish, process and store; the cesium trichloro-tri-borate birefringent crystal has moderate mechanical hardness and larger birefringence; the method can be used for manufacturing polarizing beam splitting prisms such as a gram 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. 1CsB 3 O 3 (OH) 3 Cl crystal powder XRD profile;
FIG. 2CsB 3 O 3 (OH) 3 Calculating a graph of Cl birefringence;
FIG. 3CsB 3 O 3 (OH) 3 Structure of Cl crystal;
FIG. 4 is a schematic diagram of a wedge-shaped birefringent crystal polarizing beam splitter of the present invention;
FIG. 5 is a schematic diagram of a beam displacer for crystal production grown by the method of the present invention; wherein 1 is incident light, 2 is o light, 3 is e light, 4 is optical axis, 5 is CsB 3 O 3 (OH) 3 Cl crystal, 6 light transmission direction, 7 optical axis surface.
Detailed Description
The invention is described in detail below with reference to the attached drawings and examples:
example 1
Preparation of the compound:
according to the reaction formula: csCl+3H 3 BO 3 ＝CsB 3 O 3 (OH) 3 Cl+3H 2 O synthesis compound CsB 3 O 3 (OH) 3 Cl：
CsCl and H were combined in a cesium to boron molar ratio of 1:3 3 BO 3 Weighing, placing into a mortar, adding 5mL of deionized water, grinding carefully, placing into a 100mL open glass beaker, placing into a magnetic heating stirrer, heating slowly to 80 ℃, keeping the temperature for 1 hour, taking out after the sample is dried, grinding fully to obtain single-phase polycrystalline powder of the cesium trichloro-tri-borate compound, placing into the mortar, grinding for X-ray analysis, and obtaining an X-ray spectrogram and CsB 3 O 3 (OH) 3 The X-ray spectra obtained for the Cl single crystal structure are consistent.
Example 2
Preparation of the compound:
according to the reaction formula: csOH+3H 3 BO 3 +HCl＝CsB 3 O 3 (OH) 3 Cl+4H 2 O synthesis compound CsB 3 O 3 (OH) 3 Cl：
CsOH, H was taken in a molar ratio of cesium to boron to chlorine of 1:3:1 3 BO 3 Weighing with HCl, placing into a mortar, adding 5mL deionized water, grinding, placing into 100mL corundum crucible, placing into magnetic heating stirrer, slowly heating to 85deg.C, keeping constant temperature for 1 hr, drying the sample, taking out, grinding to obtain single-phase polycrystalline powder of cesium trichlorotriborate compound, placing into mortar, grinding for X-ray analysis to obtain X-ray spectrogram and CsB 3 O 3 (OH) 3 The X-ray spectra obtained for the Cl single crystal structure are consistent.
Example 3
Preparation of the compound:
according to the reaction formula: cs (cells) 2 O+6H 3 BO 3 +2HCl＝2CsB 3 O 3 (OH) 3 Cl+7H 2 O synthesis compound CsB 3 O 3 (OH) 3 Cl：
Cs is added in a molar ratio of cesium to boron to chlorine of 1:3:1 2 O，H 3 BO 3 Weighing with HCl, placing into a mortar, adding 6mL deionized water, grinding, placing into a 100mL corundum crucible, placing into a magnetic heating stirrer, slowly heating to 80deg.C, keeping the temperature for 1.5 hr, drying the sample, taking out, grinding to obtain single-phase polycrystalline powder of cesium trichlorotriborate compound, placing into a mortar, grinding for X-ray analysis, and collecting X-ray spectrogram and CsB 3 O 3 (OH) 3 The X-ray spectra obtained for the Cl single crystal structure are consistent.
Example 4
Preparation of the compound:
according to the reaction formula: cs (cells) 2 CO 3 +6H 3 BO 3 +2HCl＝2CsB 3 O 3 (OH) 3 Cl+7H 2 O+CO 2 Synthesis of Compound CsB 3 O 3 (OH) 3 Cl：
Cs is added in a molar ratio of cesium to boron to chlorine of 1:3:1 2 CO 3 ，H 3 BO 3 Weighing with HCl, placing into a mortar, adding 7mL deionized water, grinding, placing into 100mL corundum crucible, placing into water bath, slowly heating to 90deg.C, keeping constant temperature for 4 hr, drying the sample, taking out, grinding to obtain single-phase polycrystalline powder of cesium trichlorotriborate compound, placing into mortar, grinding for X-ray analysis to obtain X-ray spectrogram and CsB 3 O 3 (OH) 3 The X-ray spectra obtained for the Cl single crystal structure are consistent.
Example 5
Preparation of the compound:
according to the reaction formula: csHCO 3 +3H 3 BO 3 +HCl＝CsB 3 O 3 (OH) 3 Cl+4H 2 O+CO 2 Synthesis of Compound CsB 3 O 3 (OH) 3 Cl：
CsHCO was prepared in a molar ratio of cesium to boron to chlorine of 1:3:1 3 ，H 3 BO 3 Weighing with HCl, placing into a mortar, adding 10mL deionized water, grinding, placing into a 100mL corundum crucible, placing into a magnetic heating stirrer, slowly heating to 95deg.C, keeping constant temperature for 3 hr, drying the sample, taking out, grinding to obtain single-phase polycrystalline powder of cesium trichlorotriborate compound, placing into a mortar, grinding for X-ray analysis to obtain X-ray spectrogram and CsB 3 O 3 (OH) 3 The X-ray spectra obtained for the Cl single crystal structure are consistent.
Example 6
Preparation of the compound:
according to the reaction formula: cs (cells) 2 SO 4 +6H 3 BO 3 +2HCl＝2CsB 3 O 3 (OH) 3 Cl+6H 2 O+H 2 SO 4 Synthesis of Compound CsB 3 O 3 (OH) 3 Cl：
Cs is added in a molar ratio of cesium to boron to chlorine of 1:3:1 2 SO 4 ，H 3 BO 3 Weighing with HCl, placing into a mortar, adding 8mL deionized water, grinding, placing into a 100mL corundum crucible, placing into a magnetic heating stirrer, slowly heating to 100deg.C, keeping constant temperature for 5 hr, drying the sample, taking out, grinding to obtain single-phase polycrystalline powder of cesium trichlorotriborate compound, placing into a mortar, grinding for X-ray analysis to obtain X-ray spectrogram and CsB 3 O 3 (OH) 3 The X-ray spectra obtained for the Cl single crystal structure are consistent.
Example 7
Preparation of the compound:
according to the reaction formula: csNO 3 +3H 3 BO 3 +HCl＝CsB 3 O 3 (OH) 3 Cl+3H 2 O+HNO 3 Synthesis of Compound CsB 3 O 3 (OH) 3 Cl：
CsNO was taken at a molar ratio of cesium to boron to chlorine of 1:3:1 3 ，H 3 BO 3 Weighing with HCl, placing into a mortar, adding 10mL deionized water, grinding, loading into 100mL corundum crucible, placing into water bath, slowly heating to 85deg.C, keeping the temperature for 3.5 hr, taking out after the sample is dried,and fully grinding to obtain single-phase polycrystalline powder of the cesium trichloro-tri-borate compound, grinding in a mortar for X-ray analysis to obtain an X-ray spectrogram and CsB 3 O 3 (OH) 3 The X-ray spectra obtained for the Cl single crystal structure are consistent.
Example 8
Room temperature solution method for growing three hydroxy chlorine three boric acid cesium double refraction crystal:
according to the reaction formula: csCl+3H 3 BO 3 ＝CsB 3 O 3 (OH) 3 Cl+3H 2 O growth of cesium tri-hydroxy chlorotrityl borate birefringent crystal:
a. CsCl and H are combined in a molar ratio Cs: b=1:3 3 BO 3 Weighing and putting the mixture into a 1000mL glass flask, adding 500mL deionized water, performing ultrasonic treatment for 5 minutes to enable the mixture to be fully mixed and dissolved, adding hydrochloric acid solution with the concentration of 37%, adjusting the pH value of the solution to be 1-3, sealing the solution by using a polyvinyl chloride film, sealing the film, pricking 20 small holes for volatilization of a solvent in the solution, and putting the glass flask into a water bath crystal growing device to obtain a mixed solution;
b. preparing seed crystals: c, keeping the mixed solution obtained in the step a at a constant temperature of 85 ℃, waiting for the solvent to volatilize, and spontaneously crystallizing to obtain seed crystals;
c. growing crystals in a solution of the compound: b, fixing the seed crystal obtained in the step b on a seed rod, putting the seed crystal into a glass flask in a water bath crystal raising device, immersing the seed crystal into the solution, keeping the constant temperature, controlling the evaporation rate of the solvent through the size and the number of small holes on the preservative film, and rotating the seed rod at a rotating speed of 10 rpm;
d. after the crystal grows to the required size, the crystal is lifted off the liquid surface and cooled to room temperature at the speed of 5 ℃/h, and then the crystal is taken out of the water bath crystal growing device, thus obtaining the CsB with the size of 24mm multiplied by 25mm multiplied by 30mm 3 O 3 (OH) 3 Cl birefringent crystal.
Example 9
Room temperature solution method for growing three hydroxy chlorine three boric acid cesium double refraction crystal:
according to the reaction formula: csOH+3H 3 BO 3 +HCl＝CsB 3 O 3 (OH) 3 Cl+4H 2 O growth of cesium tri-hydroxy chlorotrityl borate birefringent crystal:
a. CsOH and H are taken up in a molar ratio Cs:B=1:3 3 BO 3 Weighing and putting the mixture into a 1000mL glass flask, adding 500mL deionized water, performing ultrasonic treatment for 10 minutes to enable the mixture to be fully mixed and dissolved, adding hydrochloric acid solution with the concentration of 37%, adjusting the pH value of the solution to be 2-4, sealing the solution by using a polyvinyl chloride film, sealing the film, pricking 20 small holes for volatilization of a solvent in the solution, and putting the glass flask into a water bath crystal growing device to obtain a mixed solution;
b. preparing a cesium seed crystal of trihydroxy chlorotri-borate: c, keeping the mixed solution obtained in the step a at the constant temperature of 80 ℃ and waiting for the solvent to volatilize and spontaneously crystallize to obtain seed crystals;
c. growing crystals in a solution of the compound: b, fixing the seed crystal obtained in the step b on a seed rod, putting the seed crystal into a glass flask in a water bath crystal raising device, immersing the seed crystal into the solution, keeping the constant temperature, controlling the evaporation rate of the solvent through the size and the number of small holes on the preservative film, and rotating the seed rod at a rotating speed of 15 rpm;
d. after the crystal grows to the required size, the crystal is lifted off the liquid level and cooled to room temperature at the speed of 2 ℃/h, and then the crystal is taken out of the water bath crystal growing device, thus obtaining CsB of 22mm multiplied by 20mm multiplied by 30mm 3 O 3 (OH) 3 Cl birefringent crystal.
Example 10
Room temperature solution method for growing three hydroxy chlorine three boric acid cesium double refraction crystal:
according to the reaction formula: cs (cells) 2 O+6H 3 BO 3 +2HCl＝2CsB 3 O 3 (OH) 3 Cl+7H 2 O growth of cesium tri-hydroxy chlorotrityl borate birefringent crystal:
a. cs is added in a molar ratio Cs: b=1:3 2 O and H 3 BO 3 Weighing, placing into 1000mL glass flask, adding 500mL deionized water, ultrasonic treating for 15 min to make it fully mixed and dissolved, adding 37% hydrochloric acid solution, adjusting pH to 4-6, sealing with polyvinyl chloride film, andsealing the film, punching 20 small holes for volatilizing the solvent in the solution, and placing the glass flask into a water bath crystal growing device to obtain a mixed solution;
b. preparing seed crystals: c, keeping the mixed solution obtained in the step a at the constant temperature of 90 ℃ and waiting for the solvent to volatilize and spontaneously crystallize to obtain seed crystals;
c. growing crystals in a solution of the compound: b, fixing the seed crystal obtained in the step b on a seed rod, putting the seed crystal into a glass flask in a water bath crystal raising device, immersing the seed crystal into the solution, keeping the constant temperature, controlling the evaporation rate of the solvent through the size and the number of small holes on the preservative film, and rotating the seed rod at 20 rpm;
d. after the crystal grows to the required size, the crystal is lifted off the liquid surface and cooled to room temperature at the speed of 6 ℃/h, and then the crystal is taken out of the water bath crystal growing device, thus obtaining CsB of 20mm multiplied by 18mm 3 O 3 (OH) 3 Cl birefringent crystal.
Example 11
Room temperature solution method for growing three hydroxy chlorine three boric acid cesium double refraction crystal:
according to the reaction formula: cs (cells) 2 CO 3 +6H 3 BO 3 +2HCl＝2CsB 3 O 3 (OH) 3 Cl+7H 2 O+CO 2 Growing the three-hydroxy chlorine cesium triborate birefringent crystal ∈r:
a. cs is added in a molar ratio Cs: b=1:3 2 CO 3 And H 3 BO 3 Weighing and putting the mixture into a 1000mL glass flask, adding 500mL deionized water, performing ultrasonic treatment for 20 minutes to enable the mixture to be fully mixed and dissolved, adding hydrochloric acid solution with the concentration of 37%, adjusting the pH value of the solution to be 5-7, sealing the solution by using a polyvinyl chloride film, sealing the film, pricking 20 small holes for volatilization of a solvent in the solution, and putting the glass flask into a water bath crystal growing device to obtain a mixed solution;
b. preparing seed crystals: c, keeping the mixed solution obtained in the step a at a constant temperature of 85 ℃, waiting for the solvent to volatilize, and spontaneously crystallizing to obtain seed crystals;
c. growing crystals in a solution of the compound: b, fixing the seed crystal obtained in the step b on a seed rod, putting the seed crystal into a glass flask in a water bath crystal raising device, immersing the seed crystal into the solution, keeping the constant temperature, controlling the evaporation rate of the solvent through the size and the number of small holes on the preservative film, and rotating the seed rod at a rotating speed of 30 rpm;
d. after the crystal grows to the required size, the crystal is lifted off the liquid surface and cooled to room temperature at the speed of 10 ℃/h, and then the crystal is taken out of the water bath crystal growing device, thus obtaining CsB of 22mm multiplied by 18mm 3 O 3 (OH) 3 Cl birefringent crystal.
Example 12
Room temperature solution method for growing three hydroxy chlorine three boric acid cesium double refraction crystal:
according to the reaction formula: csHCO 3 +3H 3 BO 3 +HCl＝CsB 3 O 3 (OH) 3 Cl+4H 2 O+CO 2 Growing the three-hydroxy chlorine cesium triborate birefringent crystal ∈r:
a. CsHCO was added at a molar ratio Cs: b=1:3 3 And H 3 BO 3 Weighing and putting the mixture into a 1000mL glass flask, adding 500mL deionized water, performing ultrasonic treatment for 30 minutes to enable the mixture to be fully mixed and dissolved, adding hydrochloric acid solution with the concentration of 37%, adjusting the pH value of the solution to be 4-7, sealing the solution by using a polyvinyl chloride film, sealing the film, pricking 20 small holes for volatilization of a solvent in the solution, and putting the glass flask into a water bath crystal growing device to obtain a mixed solution;
b. preparing seed crystals: c, keeping the mixed solution obtained in the step a at a constant temperature of 85 ℃, waiting for the solvent to volatilize, and spontaneously crystallizing to obtain seed crystals;
c. growing crystals in a solution of the compound: b, fixing the seed crystal obtained in the step b on a seed rod, putting the seed crystal into a glass flask in a water bath crystal raising device, immersing the seed crystal into the solution, keeping the constant temperature, controlling the evaporation rate of the solvent through the size and the number of small holes on the preservative film, and rotating the seed rod at a rotating speed of 25 rpm;
d. after the crystal grows to the required size, the crystal is lifted off the liquid surface and cooled to room temperature at the speed of 10 ℃/h, and then the crystal is taken out of the water bath crystal growing device, thus obtaining CsB of 22mm multiplied by 17mm multiplied by 15mm 3 O 3 (OH) 3 Cl birefringent crystal.
Example 13
Room temperature solution method for growing three hydroxy chlorine three boric acid cesium double refraction crystal:
according to the reaction formula: cs (cells) 2 SO 4 +6H 3 BO 3 +2HCl＝2CsB 3 O 3 (OH) 3 Cl+6H 2 O+H 2 SO 4 Growth of cesium trichloro-tri-borate birefringent crystals:
a. cs is added in a molar ratio Cs: b=1:3 2 SO 4 And H 3 BO 3 Weighing and putting the mixture into a 1000mL glass flask, adding 500mL deionized water, performing ultrasonic treatment for 50 minutes to enable the mixture to be fully mixed and dissolved, adding hydrochloric acid solution with the concentration of 37%, adjusting the pH value of the solution to be 4-6, sealing the solution by using a polyvinyl chloride film, sealing the film, pricking 20 small holes for volatilization of a solvent in the solution, and putting the glass flask into a water bath crystal growing device to obtain a mixed solution;
b. preparing seed crystals: c, keeping the mixed solution obtained in the step a at a constant temperature of 85 ℃, waiting for the solvent to volatilize, and spontaneously crystallizing to obtain seed crystals;
c. growing crystals in a solution of the compound: b, fixing the seed crystal obtained in the step b on a seed rod, putting the seed crystal into a glass flask in a water bath crystal raising device, immersing the seed crystal into the solution, keeping the constant temperature, controlling the evaporation rate of the solvent through the size and the number of small holes on the preservative film, and rotating the seed rod at a rotating speed of 50 rpm;
d. after the crystal grows to the required size, the crystal is lifted off the liquid level and cooled to room temperature at the speed of 3 ℃/h, and then the crystal is taken out of the water bath crystal growing device, thus obtaining CsB of 22mm multiplied by 20mm multiplied by 15mm 3 O 3 (OH) 3 Cl birefringent crystal.
Example 14
Room temperature solution method for growing three hydroxy chlorine three boric acid cesium double refraction crystal:
according to the reaction formula: csNO 3 +3H 3 BO 3 +HCl＝CsB 3 O 3 (OH) 3 Cl+3H 2 O+HNO 3 Growth of Trihydroxy chlorideCesium triborate birefringent crystals:
a. CsNO was taken at a molar ratio Cs: b=1:3 3 And H 3 BO 3 Weighing and putting the mixture into a 1000mL glass flask, adding 500mL deionized water, performing ultrasonic treatment for 60 minutes to enable the mixture to be fully mixed and dissolved, adding hydrochloric acid solution with the concentration of 37%, adjusting the pH value of the solution to be 6-7, sealing the solution by using a polyvinyl chloride film, sealing the film, pricking 20 small holes for volatilization of a solvent in the solution, and putting the glass flask into a water bath crystal growing device to obtain a mixed solution;
b. preparing seed crystals: c, keeping the mixed solution obtained in the step a at a constant temperature of 85 ℃, waiting for the solvent to volatilize, and spontaneously crystallizing to obtain seed crystals;
c. growing crystals in a solution of the compound: b, fixing the seed crystal obtained in the step b on a seed rod, putting the seed crystal into a glass flask in a water bath crystal raising device, immersing the seed crystal into the solution, keeping the constant temperature, controlling the evaporation rate of the solvent through the size and the number of small holes on the preservative film, and rotating the seed rod at a rotating speed of 100 rpm;
d. after the crystal grows to the required size, the crystal is lifted off the liquid surface and cooled to room temperature at the speed of 1 ℃/h, and then the crystal is taken out of the water bath crystal growing device, thus obtaining the CsB with the size of 23mm multiplied by 20mm multiplied by 15mm 3 O 3 (OH) 3 Cl birefringent crystal.
Example 15:
the preparation method comprises the steps of growing the cesium trichloro-tri-borate birefringent crystal by a hydrothermal method:
a. CsCl and H are combined in a molar ratio Cs: b=1:3 3 BO 3 Weighing and mixing uniformly, putting into a clean and pollution-free hydrothermal kettle with the volume of 100mL, adding 5mL of deionized water until solute is dissolved, adding hydrochloric acid solution with the concentration of 37%, and regulating the pH value of the solution to be 4-6;
b. the reaction kettle is tightly screwed and sealed, is put into a drying oven, is heated to 130 ℃ at the speed of 50 ℃/h, is kept at the constant temperature for 48 hours, is then cooled to 25 ℃ at the speed of 1.5 ℃/h, and is opened to obtain CsB of 10mm multiplied by 5mm 3 O 3 (OH) 3 Cl birefringent crystal.
Example 16
The preparation method comprises the steps of growing the cesium trichloro-tri-borate birefringent crystal by a hydrothermal method:
a. CsOH and H are taken up in a molar ratio Cs:B=1:3 3 BO 3 Weighing and mixing uniformly, putting into a clean and pollution-free hydrothermal kettle with the volume of 100mL, adding 10mL of deionized water until solute is dissolved, adding hydrochloric acid solution with the concentration of 37%, and regulating the pH value of the solution to 3-5;
b. the reaction kettle is tightly screwed and sealed, is put into a drying oven, is heated to 160 ℃ at the speed of 30 ℃/h, is kept at the constant temperature for 40 hours, is then cooled to 25 ℃ at the speed of 1 ℃/h, and is opened to obtain CsB with the grain size of 8mm multiplied by 12mm multiplied by 4mm 3 O 3 (OH) 3 Cl birefringent crystal.
Example 17
The preparation method comprises the steps of growing the cesium trichloro-tri-borate birefringent crystal by a hydrothermal method:
a. cs is added in a molar ratio Cs: b=1:3 2 O and H 3 BO 3 Weighing and mixing uniformly, putting into a clean and pollution-free hydrothermal kettle with the volume of 100mL, adding 15mL of deionized water until solute is dissolved, adding hydrochloric acid solution with the concentration of 37%, and regulating the pH value of the solution to be 2-4;
b. the reaction kettle is tightly screwed and sealed, is put into a drying oven, is heated to 150 ℃ at the speed of 20 ℃/h, is kept at the constant temperature for 36 hours, is then cooled to 25 ℃ at the speed of 2 ℃/h, and is opened to obtain CsB of 9mm multiplied by 13mm multiplied by 4mm 3 O 3 (OH) 3 Cl birefringent crystal.
Example 18
The preparation method comprises the steps of growing the cesium trichloro-tri-borate birefringent crystal by a hydrothermal method:
a. cs is added in a molar ratio Cs: b=1:3 2 CO 3 And H 3 BO 3 Weighing and mixing uniformly, putting into a clean and pollution-free hydrothermal kettle with the volume of 100mL, adding 20mL of deionized water until solute is dissolved, adding hydrochloric acid solution with the concentration of 37%, and regulating the pH value of the solution to be 5-7;
b. the reaction kettle is tightly screwed and sealed, is put into a drying oven, is heated to 170 ℃ at the speed of 10 ℃/h, is kept at the constant temperature for 42 hours, is then cooled to 25 ℃ at the speed of 4 ℃/h, and is opened to obtain 11mm×CsB of 10mm by 5mm 3 O 3 (OH) 3 Cl birefringent crystal.
Example 19
The preparation method comprises the steps of growing the cesium trichloro-tri-borate birefringent crystal by a hydrothermal method:
a. CsHCO was added at a molar ratio Cs: b=1:3 3 And H 3 BO 3 Weighing and mixing uniformly, putting into a clean and pollution-free hydrothermal kettle with the volume of 100mL, adding 25mL of deionized water until solute is dissolved, adding hydrochloric acid solution with the concentration of 37%, and regulating the pH value of the solution to be 4-7;
b. the reaction kettle is tightly screwed and sealed, is put into a drying oven, is heated to 180 ℃ at the speed of 15 ℃/h, is kept at the constant temperature for 26 hours, is then cooled to 25 ℃ at the speed of 5 ℃/h, and is opened to obtain the CsB of 11mm multiplied by 13mm multiplied by 4mm 3 O 3 (OH) 3 Cl birefringent crystal.
Example 20
The preparation method comprises the steps of growing the cesium trichloro-tri-borate birefringent crystal by a hydrothermal method:
a. cs is added in a molar ratio Cs: b=1:3 2 SO 4 And H 3 BO 3 Weighing and mixing uniformly, putting into a clean and pollution-free hydrothermal kettle with the volume of 100mL, adding 25mL of deionized water until solute is dissolved, adding hydrochloric acid solution with the concentration of 37%, and regulating the pH value of the solution to be 6-7;
b. the reaction kettle is tightly screwed and sealed, is put into a drying oven, is heated to 220 ℃ at the speed of 30 ℃/h, is kept at the constant temperature for 18 hours, is then cooled to 25 ℃ at the speed of 4 ℃/h, and is opened to obtain CsB of 9mm multiplied by 11mm multiplied by 4mm 3 O 3 (OH) 3 Cl birefringent crystal.
Example 21
The preparation method comprises the steps of growing the cesium trichloro-tri-borate birefringent crystal by a hydrothermal method:
a. CsNO was taken at a molar ratio Cs: b=1:3 3 And H 3 BO 3 Weighing and mixing uniformly, putting into a clean and pollution-free hydrothermal kettle with the volume of 100mL, adding 25mL of deionized water until solute is dissolved, adding hydrochloric acid solution with the concentration of 37%, and regulating the pH value of the solution to be 1-4;
b. screwing and sealing the reaction kettleHeating to 190 deg.C at 15 deg.C/h, keeping the temperature for 28 hr, cooling to 25 deg.C at 2.5 deg.C/h, and opening the hydrothermal kettle to obtain CsB of 11mm×11mm×4mm 3 O 3 (OH) 3 Cl birefringent crystal.
Example 22
CsB obtained in examples 8 to 21 3 O 3 (OH) 3 The Cl birefringent crystal is used for preparing a wedge-shaped birefringent crystal polarization beam splitter, the orientation of an optical axis is shown in figure 4, a beam of natural light can be divided into two beams of linearly polarized light through the crystal after being incident, and the greater the birefringence, the farther the two beams of light can be separated, so that the separation of the beams of light is facilitated.
Example 23
Any of the CsB obtained in examples 8 to 21 3 O 3 (OH) 3 The Cl birefringent crystal is used for preparing a beam shifter, processing a birefringent crystal, and enabling the optical axis surface of the birefringent crystal to form an angle theta with the edge (shown in figure 5 a), when natural light is vertically incident, the birefringent crystal can be divided into two linearly polarized lights (shown in figure 5 b) with mutually perpendicular vibration directions, namely o light and e light, respectively, and the greater the double-fold ratio is, the farther the two lights can be separated, so that the separation of the light beams is facilitated.
Claims (7)
1. A compound cesium trichloro-tri-borate is characterized in that the molecular formula of the compound is CsB 3 O 3 (OH) 3 Cl, molecular weight 299.81, was prepared by mild solvent evaporation.
2. The method for preparing the compound cesium trichloroborate according to claim 1, which is characterized by comprising the following steps:
cesium chloride, cesium hydroxide, cesium oxide, cesium carbonate, cesium bicarbonate, cesium sulfate or cesium nitrate with 99.9% purity and boric acid or boron oxide as the boron-containing compound with 99.9% purity are weighed according to the mol ratio Cs:B=1:3, and HCI is weighed and put into a mortar, added with 5-10mL deionized water for careful grinding, then put into an open glass beaker or corundum crucible with 100mL, put into a magnetic heating stirring deviceSlowly heating to 80-100deg.C in a water bath, keeping the temperature for 1-5 hr, drying the sample, taking out, grinding to obtain single-phase polycrystalline powder of cesium trichloro-tri-borate, grinding in a mortar for X-ray analysis to obtain X-ray spectrogram and CsB 3 O 3 (OH) 3 The X-ray spectra obtained for the Cl single crystal structure are consistent.
3. A cesium tri-hydroxy-chloride tri-borate birefringent crystal is characterized in that the molecular formula of the crystal is CsB 3 O 3 (OH) 3 Cl with molecular weight of 299.81 belongs to monoclinic system, and space group isP2 1 /cUnit cell parameters a= 8.175 (3) a, b= 7.927 (2) a, c= 14.096 (4) a, β= 120.219 (17), v= 789.3 (4) a 3 ，Z=4。
4. The method for preparing the cesium trishydroxychlorotriborate birefringent crystal according to claim 3, wherein the cesium trishydroxychlorotriborate birefringent crystal is grown by a room temperature solution method or a hydrothermal method:
the room temperature solution method for growing the cesium tri-hydroxy-chloride-tri-borate birefringent crystal comprises the following steps:
a. weighing and putting a Cs-containing compound and a B-containing compound into a 1000mL glass flask according to a molar ratio of Cs to B=1 to 3, adding 500mL of deionized water, performing ultrasonic treatment for 5-60 minutes to fully mix and dissolve the Cs-containing compound and the B-containing compound, adding a hydrochloric acid solution with the concentration of 37%, adjusting the pH value of the solution to 1-7, sealing the solution by using a polyvinyl chloride film, sealing 20 small holes in the film for volatilizing a solvent in the solution, putting the glass flask into a water bath crystal growing device to obtain a mixed solution, wherein the Cs-containing compound is CsCl, csOH, cs 2 O、Cs 2 CO 3 、CsHCO 3 、Cs 2 SO 4 Or CsNO 3 The B-containing compound being H 3 BO 3 Or B is a 2 O 3 ；
b. Preparing seed crystals: c, keeping the mixed solution obtained in the step a at the constant temperature of 80-90 ℃ and waiting for the solvent to volatilize and spontaneously crystallizing to obtain seed crystals;
c. growing crystals in a solution of the compound: b, fixing the seed crystal obtained in the step b on a seed rod, putting the seed crystal into a glass flask in a water bath crystal raising device, immersing the seed crystal into the solution, keeping the constant temperature, controlling the evaporation rate of the solvent through the size and the number of small holes on the preservative film, and rotating the seed rod at a rotating speed of 0-100 rpm;
d. after the crystal grows to the required size, the crystal is lifted off the liquid level and cooled to room temperature at the speed of 1-10 ℃/h, and then the crystal is taken out of the water bath crystal-growing device, thus obtaining the CsB 3 O 3 (OH) 3 Cl birefringent crystal;
the preparation method of the cesium tri-hydroxy-chloride-tri-borate birefringent crystal by the hydrothermal method comprises the following steps:
a. weighing and uniformly mixing a Cs-containing compound and a B-containing compound according to a molar ratio of Cs to B=1 to 3, filling the mixture into a clean and pollution-free hydrothermal kettle with a volume of 100mL, adding 5-25mL of deionized water until solute is dissolved, adding a hydrochloric acid solution with a concentration of 37%, and regulating the pH value of the solution to 1-7, wherein the Cs-containing compound is CsCl, csOH, cs 2 O、Cs 2 CO 3 、CsHCO 3 、Cs 2 SO 4 Or CsNO 3 The B-containing compound being H 3 BO 3 Or B is a 2 O 3 ；
b. The reaction kettle is tightly screwed and sealed, is put into a drying oven, is heated to 100-220 ℃ at the speed of 10-30 ℃/h, is kept at the constant temperature for 10-48 hours, is then cooled to 25 ℃ at the speed of 1-5 ℃/h, and is opened to obtain the CsB 3 O 3 (OH) 3 Cl crystals.
5. Use of a cesium tri-hydroxy-chlorotrityl borate birefringent crystal according to claim 3 in the manufacture of an optical isolator, circulator, beam displacer, optical polarizer 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 splitter prism is a gram prism, a wollaston prism or a rochon prism.
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| CN113773231A (en) * | 2021-09-13 | 2021-12-10 | 中国科学院新疆理化技术研究所 | Compound hydroxyl guanidine tetrafluoroborate and hydroxyl guanidine tetrafluoroborate nonlinear optical crystal, preparation method and application |
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| CN113773231A (en) * | 2021-09-13 | 2021-12-10 | 中国科学院新疆理化技术研究所 | Compound hydroxyl guanidine tetrafluoroborate and hydroxyl guanidine tetrafluoroborate nonlinear optical crystal, preparation method and application |
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| "Hydroxyfluorooxoborate Na[B3O3F2(OH)2].[B(OH)3]: Optimizing the Optical Anisotropy with Heteroanionic Units for Deep Ultraviolet Birefringent Crystals";Jin Congcong等;《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》;第60卷(第37期);第20469-20475页 * |
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