CN114920257B - Compound cesium hexahydroxychlorotetraborate and cesium hexahydroxychlorotetraborate birefringent crystal, and preparation method and application thereof - Google Patents
Compound cesium hexahydroxychlorotetraborate and cesium hexahydroxychlorotetraborate birefringent crystal, and preparation method and application thereof Download PDFInfo
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- CN114920257B CN114920257B CN202210472500.XA CN202210472500A CN114920257B CN 114920257 B CN114920257 B CN 114920257B CN 202210472500 A CN202210472500 A CN 202210472500A CN 114920257 B CN114920257 B CN 114920257B
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- 239000013078 crystal Substances 0.000 title claims abstract description 233
- 150000001875 compounds Chemical class 0.000 title claims abstract description 64
- 229910052792 caesium Inorganic materials 0.000 title claims abstract description 55
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 29
- -1 chlorocesium tetraborate Chemical compound 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 238000000935 solvent evaporation Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 83
- 239000000460 chlorine Substances 0.000 claims description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 51
- 239000011521 glass Substances 0.000 claims description 36
- 238000000227 grinding Methods 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000005303 weighing Methods 0.000 claims description 24
- 230000003287 optical effect Effects 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 239000004570 mortar (masonry) Substances 0.000 claims description 17
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000007789 sealing Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 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
- 239000010431 corundum Substances 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000007788 liquid Substances 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
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 238000002156 mixing Methods 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
- 238000011068 loading method Methods 0.000 claims description 2
- 238000004080 punching Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000010287 polarization Effects 0.000 abstract description 4
- 238000004891 communication Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 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
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 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
- 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
- C01B35/126—Borates of alkaline-earth metals, beryllium, aluminium or magnesium
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/3551—Crystals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Abstract
The invention relates to a compound of hexahydroxy chlorocesium tetraborate and hexahydroxy chlorocesium tetraborate birefringent crystal, its preparation method and application, the molecular formula of the compound is Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl with molecular weight of 361.65 prepared by mild solvent evaporation method, and the crystal has chemical formula of Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl with molecular weight of 361.65 belongs to monoclinic system, and space group isP2 1 /cUnit cell parameters a= 8.3917 (3) a, b= 11.9993 (4) a, c= 12.7815 (4) a, β= 127.856 (2), v= 1016.18 (6) a 3 Z=4. The uv-transparent cutoff was 180. 180nm, and the birefringence was about 0.123 (532 nm). The crystal is grown by adopting a mild room temperature solution method or a hydrothermal method, and the cesium hexahydroxychlorotetraborate birefringent crystal obtained by the method 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 hexahydroxy cesium chlorotetraborate birefringent crystal, a preparation method and application thereof, in particular to a compound with a molecular formula of Cs [ B (OH) for visible light-deep ultraviolet band 3 ][B 3 O 3 (OH) 3 ]Preparation method and application of Cl hexahydroxychlorocesium tetraborate birefringent crystal
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 natural form is a birefringent crystal with wide application range, but has high impurity content, common crystal can only use wave band above 350nm, ultraviolet light grade calcite crystal is difficult to obtain, and the use wave band can not reach deep ultraviolet region<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 present invention aims at providing one kind of compound, namely, cesium hexahydroxychlorotetraborate and cesium hexahydroxychlorotetraborate birefringent crystal, with the molecular formula being Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl, molecular weight 361.65, was prepared by mild solvent evaporation. The molecular formula of the crystal is Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl with molecular weight of 361.65 belongs to monoclinic system, and the space group is P2 1 Unit cell parameters/cβ＝ 127.856(2)，/>Z＝4。
Another object of the present invention is to provide a method for preparing large-sized cesium hexahydroxychlorotetraborate birefringent crystals.
It is a further object of the present invention to provide the use of cesium hexahydroxychlorotetraborate birefringent crystals.
The invention relates to a compound of hexahydroxy cesium chlorotetraborate, the molecular formula of which is Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl, molecular weight 361.65, was prepared by mild solvent evaporation.
The preparation method of the compound cesium hexahydroxychlorotetraborate comprises the following steps:
adding cesium-containing compound with purity of 99.9% such as cesium chloride, cesium hydroxide, cesium oxide, cesium carbonate, cesium bicarbonate, cesium sulfate or cesium nitrate and boron-containing compound with purity of 99.9% such as boric acid or boron oxide into a mortar according to a molar ratio of Cs:B=1:4, adding 5-10mL of deionized water for careful grinding, then placing into a 100mL open glass beaker or corundum crucible, placing 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 the sample is dried, grinding sufficiently to obtain single-phase polycrystalline powder of the hexahydroxy cesium chloride tetraborate compound, and then placing into the mortar for grinding for X-ray analysis to obtain an X-ray spectrogram and Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]The X-ray spectra obtained for the Cl single crystal structure are consistent.
Cesium hexahydroxychlorotetraborate birefringent crystal with molecular formula of Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl with molecular weight of 361.65 belongs to monoclinic system, and the space group is P2 1 Unit cell parameters/c β＝127.856(2)，Z＝4。
The preparation method of the cesium hexahydroxychlorotetraborate birefringent crystal adopts a room temperature solution method or a hydrothermal method to grow the crystal;
the room temperature solution method for growing the cesium hexahydroxychlorotetraborate birefringent crystal comprises the following steps:
a. cs-containing compound and B-containing compound were weighed into a 1000mL glass flask at a molar ratio Cs: B=1:4, and 500mL was addedDeionized water, ultrasonic treating for 5-60 min to make them fully mixed and dissolved, adding hydrochloric acid solution whose concentration is 37%, regulating pH value of solution to 1-7, sealing with polyvinyl chloride film, pricking 20 small holes in film seal for volatilizing solvent in the solution, placing glass flask into water bath crystal-raising device to obtain mixed solution, the compound containing Cs 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, 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 surface 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 Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl birefringent crystal;
the preparation method of the cesium hexahydroxychlorotetraborate birefringent crystal by the hydrothermal method comprises the following steps of:
a. weighing and uniformly mixing a Cs-containing compound and a B-containing compound according to a molar ratio Cs:B=1:4, 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 box, 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 Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl crystals.
The application of the cesium hexahydroxychlorotetraborate 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 invention relates to a preparation method of a compound of cesium hexahydroxychlorotetraborate and cesium hexahydroxychlorotetraborate birefringent crystal, which adopts a mild solvent evaporation method to synthesize the compound, and grows the cesium hexahydroxychlorotetraborate birefringent crystal by a room-temperature solution method or a hydrothermal method, wherein the chemical reaction formula of the compound is as follows:
CsCl+4H 3 BO 3 ＝Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+3H 2 O；
CsOH+4H 3 BO 3 +HCl＝Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+4H 2 O；
Cs 2 O+8H 3 BO 3 +2HCl＝2Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+7H 2 O；
Cs 2 CO 3 +8H 3 BO 3 +2HCl＝2Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+7H 2 O+CO 2 ↑；
CsHCO 3 +4H 3 BO 3 +HCl＝Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+4H 2 O+CO 2 ↑；
Cs 2 SO 4 +8H 3 BO 3 +2HCl＝2Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+6H 2 O+H 2 SO 4 ；
CsNO 3 +4H 3 BO 3 +HCl＝Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+3H 2 O+HNO 3 。
the chemical formula of the cesium hexahydroxychlorotetraborate birefringent crystal is Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl with molecular weight of 361.65 belongs to monoclinic system, and the space group is P2 1 Unit cell parameters/c β＝127.856(2)，Z=4. The crystal is used in visible light-deep ultraviolet band, the ultraviolet transmission cut-off edge is 180nm, and the double refraction index is about 0.123 (532 nm). The crystal is easy to grow, cut, polish, process and store; the preparation method adopts a mild solvent evaporation method for synthesis; cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]The Cl birefringent crystal grows by adopting a room temperature solution method or a hydrothermal method, and the hexahydroxy cesium chlorotetraborate birefringent crystal obtained by the method 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. 1 is Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl crystal powder XRD profile;
FIG. 2 is Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Calculating a graph of Cl birefringence;
FIG. 3 is Cs [ B (OH) 3 ][B 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 Cs [ B (OH) 3 ][B 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+4H 3 BO 3 ＝Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+3H 2 O Synthesis of Compound Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl：
CsCl and H were combined in a cesium to boron molar ratio of 1:4 3 BO 3 Weighing, putting into a mortar, adding 5mL of deionized water, grinding carefully, then putting into a 100mL open glass beaker or corundum crucible, putting into a magnetic heating stirrer, heating slowly to 80 ℃, keeping the temperature for 1 hour, taking out the sample after the sample is dried, taking out the sample and grinding fully to obtain single-phase polycrystalline powder of the hexahydroxy chlorocesium tetraborate compound, putting into the mortar, grinding for X-ray analysis, and obtaining an X-ray spectrogram and Cs [ B (OH) 3 ][B 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+4H 3 BO 3 +HCl＝Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+4H 2 O Synthesis of Compound Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl：
CsOH, H was taken in a molar ratio of cesium to boron to chlorine of 1:4:1 3 BO 3 Weighing with HCl, placing into a mortar, adding 5mL deionized water, grinding, placing into 100mL open glass beaker or corundum crucible, placing into a water bath, slowly heating to 85deg.C, keeping the temperature for 1 hr, taking out after the sample is dried, taking out and grinding sufficiently to obtain single-phase polycrystalline powder of hexahydroxy cesium chlorotetraborate compound, placing into a mortar, grinding for X-ray analysis, and obtaining X-ray spectrogram and Cs [ B (OH) 3 ][B 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+8H 3 BO 3 +2HCl＝2Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+7H 2 O Synthesis of Compound Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl：
Cs is added in a molar ratio of cesium to boron to chlorine of 1:4:1 2 O，H 3 BO 3 Weighing with HCl, placing into a mortar, adding 5mL deionized water, grinding, placing into 100mL open glass beaker or corundum crucible, placing into a magnetic heating stirrer, slowly heating to 80deg.C, keeping the temperature for 1.5 hr, taking out after the sample is dried, taking out and grinding sufficiently to obtain single-phase polycrystalline powder of hexahydroxy cesium chlorotetraborate compound, placing into a mortar, grinding for X-ray analysis, and obtaining X-ray spectrogram and Cs [ B (OH) 3 ][B 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 +8H 3 BO 3 +2HCl＝2Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+7H 2 O+CO 2 Synthesis of Compound Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl：
Cs is added in a molar ratio of cesium to boron to chlorine of 1:4:1 2 CO 3 ，H 3 BO 3 Weighing with HCl, placing into a mortar, adding 5mL deionized water, grinding, placing into 100mL open glass beaker or corundum crucible, placing into a water bath, slowly heating to 90deg.C, keeping constant temperature for 4 hr, taking out after the sample is dried, taking out and grinding sufficiently to obtain single-phase polycrystalline powder of hexahydroxy chlorocesium tetraborate compound, placing into a mortar, grinding for X-ray analysis, and obtaining X-ray spectrogram and Cs [ B (OH) 3 ][B 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 +4H 3 BO 3 +HCl＝Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+4H 2 O+CO 2 Synthesis of Compound Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl：
CsHCO was prepared in a molar ratio of cesium to boron to chlorine of 1:4:1 3 ，H 3 BO 3 Weighing with HCl, placing into a mortar, adding 10mL deionized water, grinding, placing into 100mL open glass beaker or corundum crucible, placing into a water bath, slowly heating to 95deg.C, keeping constant temperature for 3 hr, taking out after the sample is dried, taking out and grinding sufficiently to obtain single-phase polycrystalline powder of hexahydroxy chlorocesium tetraborate compound, placing into a mortar, grinding for X-ray analysis, and obtaining X-ray spectrogram and Cs [ B (OH) 3 ][B 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 +8H 3 BO 3 +2HCl＝2Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+6H 2 O+H 2 SO 4 Synthesis of Compound Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl：
Cs is added in a molar ratio of cesium to boron to chlorine of 1:4:1 2 SO 4 ，H 3 BO 3 Weighing with HCl, placing into a mortar, adding 10mL deionized water, grinding, placing into 100mL open glass beaker or corundum crucible, placing into a magnetic heating stirrer, slowly heating to 100deg.C, keeping the temperature for 5 hr, taking out after the sample is dried, taking out and grinding sufficiently to obtain single-phase polycrystalline powder of hexahydroxy cesium chlorotetraborate compound, placing into a mortar, grinding for X-ray analysis, and obtaining X-ray spectrogram and Cs [ B (OH) 3 ][B 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 +4H 3 BO 3 +HCl＝Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+3H 2 O+HNO 3 Synthesis of Compound Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl：
CsNO was taken at a molar ratio of cesium to boron to chlorine of 1:4:1 3 ，H 3 BO 3 Weighing with HCl, grinding with 10mL deionized water, loading into 100mL open glass beaker or corundum crucible, placing into magnetic heating stirrer, slowly heating to 85deg.C, keeping constant temperature for 3.5 hr, taking out after the sample is dried, taking out and grinding to obtain single-phase polycrystalline powder of hexahydroxy cesium chlorotetraborate compound, grinding in mortar for X-ray analysis to obtain X-ray spectrogram and Cs [ B (OH) 3 ][B 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 hexahydroxy chlorine cesium tetraborate birefringent crystal:
according to the reaction formula: csCl+4H 3 BO 3 ＝Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+3H 2 O growth of cesium hexahydroxychlorotetraborate birefringent crystals:
a. CsCl and H are combined in a molar ratio Cs: b=1:4 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, 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 Cs [ B (OH) with the size of 24mm multiplied by 20mm multiplied by 30mm 3 ][B 3 O 3 (OH) 3 ]Cl birefringent crystal.
Example 9
Room temperature solution method for growing hexahydroxy chlorine cesium tetraborate birefringent crystal:
according to the reaction formula: csOH+4H 3 BO 3 +HCl＝Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+4H 2 O growth of cesium hexahydroxychlorotetraborate birefringent crystals:
a. CsOH and H were combined in a molar ratio Cs:B=1:4 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 seed crystals: 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, 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 surface 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 Cs [ B (OH) of 22mm multiplied by 20mm multiplied by 25mm 3 ][B 3 O 3 (OH) 3 ]Cl birefringent crystal.
Example 10
Room temperature solution method for growing hexahydroxy chlorine cesium tetraborate birefringent crystal:
according to the reaction formula: cs (cells) 2 O+8H 3 BO 3 +2HCl＝2Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+7H 2 O growth of cesium hexahydroxychlorotetraborate birefringent crystals:
a. cs is added in a molar ratio Cs: b=1:4 2 O and H 3 BO 3 Weighing and putting the mixture into a 1000mL glass flask, adding 500mL deionized water, performing ultrasonic treatment for 15 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 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, 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 Cs [ B (OH) of 20mm multiplied by 23mm multiplied by 18mm 3 ][B 3 O 3 (OH) 3 ]Cl birefringent crystal.
Example 11
Room temperature solution method for growing hexahydroxy chlorine cesium tetraborate birefringent crystal:
according to the reaction formula: cs (cells) 2 CO 3 +8H 3 BO 3 +2HCl＝2Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+7H 2 O+CO 2 Growing a cesium hexahydroxychlorotetraborate birefringent crystal ∈r:
a. cs is added in a molar ratio Cs: b=1:4 2 CO 3 And H 3 BO 3 Weighing, placing into 1000mL glass flask, adding 500mL deionized water, performing ultrasonic treatment for 20 min to obtain a mixture, dissolving, and adding 37% hydrochloric acid solutionRegulating the pH value of the solution to 5-7, sealing with a polyvinyl chloride film, pricking 20 small holes in the film 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 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, 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 Cs [ B (OH) with the size of 22mm multiplied by 18mm multiplied by 24mm 3 ][B 3 O 3 (OH) 3 ]Cl birefringent crystal.
Example 12
Room temperature solution method for growing hexahydroxy chlorine cesium tetraborate birefringent crystal:
according to the reaction formula: csHCO 3 +4H 3 BO 3 +HCl＝Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+4H 2 O+CO 2 Growing hexahydroxy chlorine cesium tetraborate crystals ∈:
a. CsHCO was added at a molar ratio Cs: b=1:4 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, 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 Cs [ B (OH) of 22mm multiplied by 17mm multiplied by 19mm 3 ][B 3 O 3 (OH) 3 ]Cl birefringent crystal.
Example 13
Room temperature solution method for growing hexahydroxy chlorine cesium tetraborate birefringent crystal:
according to the reaction formula: cs (cells) 2 SO 4 +8H 3 BO 3 +2HCl＝2Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+6H 2 O+H 2 SO 4 Growing hexahydroxy chlorine cesium tetraborate crystals:
a. cs is added in a molar ratio Cs: b=1:4 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, 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 surface 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 Cs [ B (OH) of 22mm multiplied by 20mm multiplied by 17mm 3 ][B 3 O 3 (OH) 3 ]Cl birefringent crystalA body.
Example 14
Room temperature solution method for growing hexahydroxy chlorine cesium tetraborate birefringent crystal:
according to the reaction formula: csNO 3 +4H 3 BO 3 +HCl＝Cs[B(OH) 3 ][B 3 O 3 (OH) 3 ]Cl+3H 2 O+HNO 3 Growing hexahydroxy chlorine cesium tetraborate crystals:
a. CsNO was taken at a molar ratio Cs: b=1:4 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, 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 Cs [ B (OH) with the size of 23mm multiplied by 20mm multiplied by 16mm 3 ][B 3 O 3 (OH) 3 ]Cl birefringent crystal.
Example 15
Growing the cesium hexahydroxychlorotetraborate birefringent crystal by a hydrothermal method:
a. CsCl and H are combined in a molar ratio Cs: b=1:4 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, placed in a drying oven, heated to 130 ℃ at the speed of 50 ℃/h, kept at constant temperature for 48 hours, then cooled to 25 ℃ at the speed of 1.5 ℃/h, and the hydrothermal kettle is opened, thus obtaining Cs [ B (OH) of 10mm multiplied by 7mm multiplied by 5mm 3 ][B 3 O 3 (OH) 3 ]Cl birefringent crystal.
Example 16
Growing the cesium hexahydroxychlorotetraborate birefringent crystal by a hydrothermal method:
a. CsOH and H were combined in a molar ratio Cs:B=1:4 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 and is kept at the constant temperature for 40 hours, then is cooled to 25 ℃ at the speed of 1 ℃/h, and is opened, thus obtaining Cs [ B (OH) of 8mm multiplied by 10mm multiplied by 4mm 3 ][B 3 O 3 (OH) 3 ]Cl birefringent crystal.
Example 17
Growing the cesium hexahydroxychlorotetraborate birefringent crystal by a hydrothermal method:
a. cs is added in a molar ratio Cs: b=1:4 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 and is kept at the constant temperature for 36 hours, then is cooled to 25 ℃ at the speed of 2 ℃/h, and is opened, thus obtaining Cs [ B (OH) of 9mm multiplied by 11mm multiplied by 4mm 3 ][B 3 O 3 (OH) 3 ]Cl birefringent crystal.
Example 18
Growing the cesium hexahydroxychlorotetraborate birefringent crystal by a hydrothermal method:
a. cs is added in a molar ratio Cs: b=1:4 2 CO 3 And H 3 BO 3 Weighing and mixingUniformly placing the solution 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 adjusting the pH value of the solution to 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 and is kept at constant temperature for 42 hours, then is cooled to 25 ℃ at the speed of 4 ℃/h, and is opened, thus obtaining Cs [ B (OH) of 11mm multiplied by 5mm 3 ][B 3 O 3 (OH) 3 ]Cl birefringent crystal.
Example 19
Growing the cesium hexahydroxychlorotetraborate birefringent crystal by a hydrothermal method:
a. CsHCO was added at a molar ratio Cs: b=1:4 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 and is kept at the constant temperature for 26 hours, then is cooled to 25 ℃ at the speed of 5 ℃/h, and is opened, thus obtaining Cs [ B (OH) of 11mm multiplied by 13mm multiplied by 3mm 3 ][B 3 O 3 (OH) 3 ]Cl birefringent crystal.
Example 20
Growing the cesium hexahydroxychlorotetraborate birefringent crystal by a hydrothermal method:
a. cs is added in a molar ratio Cs: b=1:4 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 and is kept at the constant temperature for 18 hours, then is cooled to 25 ℃ at the speed of 4 ℃/h, and is opened, thus obtaining Cs [ B (OH) of 9mm multiplied by 7mm multiplied by 4mm 3 ][B 3 O 3 (OH) 3 ]Cl birefringent crystal.
Example 21
Growing the cesium hexahydroxychlorotetraborate birefringent crystal by a hydrothermal method:
a. CsNO was taken at a molar ratio Cs: b=1:4 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. the reaction kettle is tightly screwed and sealed, placed in a drying oven, heated to 190 ℃ at the speed of 15 ℃/h, kept at constant temperature for 28 hours, then cooled to 25 ℃ at the speed of 2.5 ℃/h, and the hydrothermal kettle is opened, thus obtaining Cs [ B (OH) of 11mm multiplied by 8mm multiplied by 4mm 3 ][B 3 O 3 (OH) 3 ]Cl birefringent crystal.
Example 22
Cs [ B (OH) of examples 8-21 3 ][B 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 Cs [ B (OH) obtained in examples 8-21 3 ][B 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 hexahydroxychlorotetraborate is characterized in that the molecular formula of the compound is Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl, molecular weight 361.65, was prepared by mild solvent evaporation.
2. The method for preparing the compound cesium hexahydroxychlorotetraborate according to claim 1, which is characterized by comprising the following steps:
adding cesium-containing compound with purity of 99.9% such as cesium chloride, cesium hydroxide, cesium oxide, cesium carbonate, cesium bicarbonate, cesium sulfate or cesium nitrate, boric acid or boron oxide as boron-containing compound with purity of 99.9% and HCI into a mortar according to a molar ratio of Cs:B=1:4, adding 5-10mL deionized water for careful grinding, loading into a 100mL open glass beaker or corundum crucible, placing into a magnetic heating stirrer or water bath, slowly heating to 80-100 ℃ for 1-5 hours at constant temperature, taking out after a sample is dried, grinding sufficiently to obtain single-phase polycrystalline powder of hexahydroxychlorocesium tetraborate compound, and then placing into a mortar for grinding for X-ray analysis to obtain an X-ray spectrogram and Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]The X-ray spectra obtained for the Cl single crystal structure are consistent.
3. The hexahydroxy chlorine cesium tetraborate birefringent crystal is characterized in that the molecular formula of the crystal is Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl with molecular weight of 361.65 belongs to monoclinic system, and space group isP2 1 /cUnit cell parameters a= 8.3917 (3) a, b= 11.9993 (4) a, c= 12.7815 (4) a, β= 127.856 (2), v= 1016.18 (6) a 3 ，Z=4。
4. The method for preparing the cesium hexahydroxychlorotetraborate birefringent crystal according to claim 3, wherein the crystal is grown by a room temperature solution method or a hydrothermal method;
the room temperature solution method for growing the cesium hexahydroxychlorotetraborate birefringent crystal comprises the following steps:
a. weighing Cs-containing compound and B-containing compound according to a molar ratio of Cs to B=1 to 4, putting the Cs-containing compound and the B-containing compound into a 1000mL glass flask, adding 500mL of deionized water, carrying out 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%, regulating the pH value of the solution to be 1-7, sealing the solution by using a polyvinyl chloride film,and sealing the film and 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, wherein the compound containing Cs 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, 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 surface 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 Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl birefringent crystal;
the preparation method of the cesium hexahydroxychlorotetraborate birefringent crystal by the hydrothermal method comprises the following steps of:
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 4, 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 adjusting 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 box, 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 Cs [ B (OH) 3 ][B 3 O 3 (OH) 3 ]Cl crystals.
5. Use of a cesium hexahydroxychlorotetraborate birefringent crystal according to claim 3 for the preparation of an optical isolator, circulator, beam shifter, 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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| CN103696006A (en) * | 2012-09-28 | 2014-04-02 | 中国科学院新疆理化技术研究所 | Monohydrate hydroxyl strontium borate and monohydrate hydroxyl strontium borate nonlinear optical crystal, and preparation method and application of monohydrate hydroxyl strontium borate nonlinear optical crystal |
| CN104562197A (en) * | 2013-10-23 | 2015-04-29 | 中国科学院新疆理化技术研究所 | Compound mono-boric dihydroxyl barium decaborate monohydrate nonlinear optical crystal and preparation method and use thereof |
| CN114016132A (en) * | 2021-11-13 | 2022-02-08 | 中国科学院新疆理化技术研究所 | Barium pentahydrate pentahydroxyl tridecanoate, barium pentahydrate pentahydroxyl tridecanoate nonlinear optical crystal, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103696006A (en) * | 2012-09-28 | 2014-04-02 | 中国科学院新疆理化技术研究所 | Monohydrate hydroxyl strontium borate and monohydrate hydroxyl strontium borate nonlinear optical crystal, and preparation method and application of monohydrate hydroxyl strontium borate nonlinear optical crystal |
| CN104562197A (en) * | 2013-10-23 | 2015-04-29 | 中国科学院新疆理化技术研究所 | Compound mono-boric dihydroxyl barium decaborate monohydrate nonlinear optical crystal and preparation method and use thereof |
| CN114016132A (en) * | 2021-11-13 | 2022-02-08 | 中国科学院新疆理化技术研究所 | Barium pentahydrate pentahydroxyl tridecanoate, barium pentahydrate pentahydroxyl tridecanoate nonlinear optical crystal, preparation method and application |
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