CN111945228B - Birefringent crystal material, preparation method and application thereof - Google Patents
Birefringent crystal material, preparation method and application thereof Download PDFInfo
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- CN111945228B CN111945228B CN201910400046.5A CN201910400046A CN111945228B CN 111945228 B CN111945228 B CN 111945228B CN 201910400046 A CN201910400046 A CN 201910400046A CN 111945228 B CN111945228 B CN 111945228B
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- 239000013078 crystal Substances 0.000 title claims abstract description 169
- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002178 crystalline material Substances 0.000 claims abstract description 45
- 230000003287 optical effect Effects 0.000 claims abstract description 25
- 238000002834 transmittance Methods 0.000 claims abstract description 13
- 238000010521 absorption reaction Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000011575 calcium Substances 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 239000011777 magnesium Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 22
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 229910052701 rubidium Inorganic materials 0.000 claims description 9
- 238000001228 spectrum Methods 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 8
- 239000000920 calcium hydroxide Substances 0.000 claims description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- -1 potassium fluoroborate Chemical compound 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims description 8
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims description 8
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 7
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 6
- 239000001095 magnesium carbonate Substances 0.000 claims description 6
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 6
- 239000000347 magnesium hydroxide Substances 0.000 claims description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- 230000003595 spectral effect Effects 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 5
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 claims description 4
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 claims description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 4
- WFUBYPSJBBQSOU-UHFFFAOYSA-M rubidium iodide Chemical compound [Rb+].[I-] WFUBYPSJBBQSOU-UHFFFAOYSA-M 0.000 claims description 4
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 claims description 3
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- 229910001640 calcium iodide Inorganic materials 0.000 claims description 2
- 229940046413 calcium iodide Drugs 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001641 magnesium iodide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 229940102127 rubidium chloride Drugs 0.000 claims description 2
- 229910001952 rubidium oxide Inorganic materials 0.000 claims description 2
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 2
- 238000004891 communication Methods 0.000 abstract description 3
- 238000001259 photo etching Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000010586 diagram Methods 0.000 description 7
- QWVYNEUUYROOSZ-UHFFFAOYSA-N trioxido(oxo)vanadium;yttrium(3+) Chemical compound [Y+3].[O-][V]([O-])([O-])=O QWVYNEUUYROOSZ-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940031958 magnesium carbonate hydroxide Drugs 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001419 rubidium ion Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
Images
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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
- C30B29/54—Organic compounds
-
- 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
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a birefringent crystal material, a preparation method and application thereof. The crystalline material has the chemical formula A2B(H2C3N3O3)4·4H2O, wherein A is selected from K and/or Rb; b is selected from Mg and/or Ca; the crystal material belongs to a monoclinic system, and the space group is C2/m. The ultraviolet absorption cut-off wavelength of the crystal material is about 237nm, and the crystal material has higher transmittance in the range of 200-2500 nm. The birefringence of the crystal material is about 0.3 under 800nm, is a birefringent crystal material with potential application value, can be used for manufacturing polarizing prisms, electro-optical adjusting switches and the like, and has application in optical communication, micro-processing, photoetching and other aspects.
Description
Technical Field
The invention belongs to the field of crystal materials, and particularly relates to a birefringent crystal, and a preparation method and application thereof.
Background
When a light beam is projected on a crystal interface, two refracted light beams are generally generated, the phenomenon is called birefringence, the main reason for generating the birefringence phenomenon is due to the anisotropy of crystal materials, the included angle of the two refracted light beams is related to the propagation direction and the polarization state of the two refracted light beams, the crystal capable of generating the birefringence phenomenon is called as a birefringence crystal, and the birefringence crystal acts like a polarizer with two transmission directions vertical to each other. Birefringence is an important optical performance index for judging electro-optical functional crystal materials. The linearly polarized light can be obtained by utilizing the birefringent crystal, the linearly polarized light is widely applied in the optical field at present, for example, the fields of photoetching, communication, micromachining and the like, at present, the number of the birefringent crystals at home and abroad is thousands, but the number of the birefringent crystals capable of really realizing the manufacture of the polarizing device is small, mainly because the requirements of the polarizing prism on the birefringent crystals are strict, and several requirements are generally required to be met: (1) the structure of the crystal is preferably uniaxial; (2) the crystal has larger birefringence in the use waveband; (3) defects without optical grade requirements, namely no inclusion, cracks and the like; (4) easily growing and obtaining a large-sized single crystal; (5) the physicochemical property is stable; (6) is not easy to deliquesce; (7) the laser damage resistance threshold is high.
Birefringent crystals that have been commercialized to date are, among others, cryolite, lithium niobate, yttrium vanadate, rutile, magnesium fluoride, and high temperature phase barium metaborate. For the ice winter stone, the transmission range is wider and the refractive index is larger, but the manufacturing process is complex, the artificial growth is difficult, large-size single crystals cannot be obtained, in addition, the ice winter stone has serious absorption below 350nm, and a polarizing device cannot be applied to an ultraviolet deep ultraviolet region and can only be applied to visible and infrared bands. For yttrium vanadate crystals, the transmittance of the yttrium vanadate crystals in an ultraviolet band below 400nm is poor, so that the yttrium vanadate crystals cannot be applied in an ultraviolet deep ultraviolet band, and in addition, the laser damage threshold of the yttrium vanadate crystals in a visible band is low, so that the yttrium vanadate crystals can only be applied in a middle infrared band. The magnesium fluoride crystal belongs to a tetragonal system, has a wide transmission range of 110nm-8500nm, is the only birefringent crystal capable of being used in ultraviolet deep ultraviolet band, but has a serious defect that the birefringence is relatively low, so that the magnesium fluoride crystal has the defect of overlarge volume if used as a polarizing device. Also suffering from refractive index are silica crystals, so they are not suitable as polarizing devices. For the high-temperature phase barium metaborate, the high-temperature phase barium metaborate has a wider spectrum transmission range (189-3500nm), a shorter ultraviolet cut-off edge (189nm), a larger birefringence (0.159@253.7nm) and a high laser damage threshold, and has important application value in an ultraviolet region. However, the transmittance of the crystal at 193nm is less than 40%. And the crystal has phase change at high temperature, and is easy to crack in the growth process, and the defects influence the application of the crystal.
With the development of science and technology, the requirement of birefringent crystals is higher and higher, both qualitatively and quantitatively, so that it is very important to find an excellent birefringent crystal. The excellent birefringent crystal is required to be easy to process and grow, and has a large birefringence and transmittance, and the physicochemical properties are stable, so researchers have been continuously searching and trying in recent years to find an excellent birefringent crystal material and use the material in practical applications.
Disclosure of Invention
In one aspect of the present invention, a crystalline material is provided having a formula A2B(H2C3N3O3)4·4H2O, wherein A is selected from K and/or Rb; b is selected from Mg and/or Ca;
the crystal material belongs to a monoclinic system, and the space group is C2/m.
According to an exemplary embodiment of the present invention, the crystalline material is K2Mg(H2C3N3O3)4·4H2O, the unit cell parameters of which are:
α ═ γ ═ 90 °, β ═ 116.876 °. Preferably, said K2Mg(H2C3N3O3)4·4H2The O crystal material has a crystal structure as shown in fig. 1 (b). Preferably, said K2Mg(H2C3N3O3)4·4H2The O crystal material has an XRD spectrum substantially as shown in fig. 2 (b).
According to an exemplary embodiment of the present invention, the crystalline material is K2Ca(H2C3N3O3)4·4H2O, the unit cell parameters of which are:
α ═ γ ═ 90 °, β ═ 99.574 °. Preferably, said K2Ca(H2C3N3O3)4·4H2The O crystal material has a crystal structure as shown in fig. 1 (a). Preferably, said K2Ca(H2C3N3O3)4·4H2The O crystal material has an XRD spectrum substantially as shown in fig. 2 (a).
According to an exemplary embodiment of the present invention, the crystalline material is Rb2Ca(H2C3N3O3)4·4H2O, the unit cell parameters are:
α ═ γ ═ 90 °, β ═ 99.950 °. Preferably, said Rb is2Ca(H2C3N3O3)4·4H2The O crystal material has a crystal structure as shown in fig. 1 (c). Preferably, said Rb is2Ca(H2C3N3O3)4·4H2The O crystal material has an XRD spectrum substantially as shown in fig. 2 (c).
The crystalline material according to the invention has a crystal structure in which every two adjacent [ H ] s2C3N3O3]-The groups are connected through hydrogen bonds (H-N … H), and A ions and B ions are filled in [ H ]2C3N3O3]-The groups form a band-shaped structure.
According to the crystalline material of the present invention, the birefringence of the crystalline material at 800nm is 0.3-0.4, such as 0.35-0.4, as an example, the birefringence is 0.362, 0.376.
According to the crystal material provided by the invention, the transmittance of the crystal material in the spectral range of 200-2500nm is more than 85%, and the crystal material has high transmittance.
According to the crystal material of the invention, the ultraviolet absorption cut-off wavelength of the crystal material is about 237nm, such as 230-240nm, and as an example, the ultraviolet absorption cut-off wavelength is 231nm, 235nm or 236 nm.
According to the crystal material of the present invention, the crystal material is a colorless transparent crystal.
In still another aspect of the present invention, there is provided a method for preparing the crystalline material, the method comprising the steps of: mixing a compound containing potassium element and/or rubidium element, a compound containing calcium element and/or magnesium element, cyanuric acid and water by adopting an aqueous solution method, heating, and then cooling and crystallizing to obtain the crystal material.
According to the preparation method, the molar volume ratio of the potassium element and/or the rubidium element, the calcium element and/or the magnesium element, the cyanuric acid and the water is (0.1-20) mmol, (0.3-50) mmol, (0.2-90) mmol and (5-100) mL. Preferably, the molar volume ratio is (0.1-10) mmol, (0.3-30) mmol, (0.2-80) mL, more preferably (0.1-1) mmol, (0.3-1) mmol, (0.2-2) mL. Illustratively, the molar volume ratio is 0.2mmol:0.4mmol:100mL, 0.4mmol:0.2mmol:0.8mmol:100mL, 0.4mmol:0.2mmol:1mmol:80mL, 0.4mmol:0.2mmol:1.2mmol:70mL, 0.4mmol:0.2mmol:0.8mmol:70mL, 0.4mmol: 0.8mmol:60 mL.
According to the preparation method of the present invention, the heating temperature is 40 to 100 ℃, for example, 60 to 100 ℃; illustratively, the temperature may be 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 100 ℃. Preferably, the degree of heating is: until the volume of the mixed liquor is reduced to 45-95%, for example 50-90%, of the initial volume of the mixed liquor, illustratively, the heating is performed until the volume of the mixed liquor is reduced to 50%, 60%, 70%, 80%, or 90% of the initial volume of the mixed liquor.
According to the production method of the present invention, the potassium element-containing compound may be at least one selected from the group consisting of potassium nitrate, potassium chloride, potassium oxide, potassium fluoride, potassium iodide, potassium carbonate, potassium hydroxide, potassium fluoroborate, and the like. Preferably, the potassium element-containing compound may be at least one selected from potassium nitrate, potassium carbonate, and potassium hydroxide. Illustratively, the potassium element-containing compound may be selected from potassium nitrate, potassium carbonate, or potassium hydroxide.
According to the production method of the present invention, the rubidium element-containing compound may be at least one selected from the group consisting of rubidium nitrate, rubidium chloride, rubidium oxide, rubidium fluoride, rubidium iodide, rubidium carbonate, rubidium hydroxide, rubidium fluoroborate, and the like. Preferably, the rubidium element-containing compound may be selected from rubidium nitrate and/or rubidium carbonate. Illustratively, the rubidium-element-containing compound may be selected from rubidium carbonate.
According to the preparation method of the present invention, the calcium element-containing compound may be at least one selected from the group consisting of calcium nitrate, calcium chloride, calcium oxide, calcium fluoride, calcium iodide, calcium carbonate, calcium hydroxide, calcium fluoroborate, and the like. Preferably, the calcium element-containing compound may be selected from at least one of calcium nitrate, calcium carbonate, and calcium hydroxide. Illustratively, the calcium element-containing compound may be selected from calcium carbonate or calcium hydroxide.
According to the preparation method of the present invention, the magnesium element-containing compound may be at least one selected from magnesium nitrate, magnesium chloride, magnesium oxide, magnesium fluoride, magnesium iodide, magnesium carbonate, magnesium hydroxide, magnesium fluoroborate, and the like. Preferably, the magnesium element-containing compound may be at least one selected from magnesium nitrate, magnesium carbonate, and magnesium hydroxide. Illustratively, the elemental magnesium-containing compound may be selected from magnesium carbonate or magnesium hydroxide.
In a further aspect of the invention, there is provided the use of the crystalline material as a birefringent crystalline material.
In yet another aspect of the invention, there is provided the use of the crystalline material in an optical device. Preferably, the optical device may be an optical polarizer, a beam displacer, a circulator, an optical isolator or an optical modulator.
In a further aspect of the invention there is provided an optical polariser comprising the crystalline material described above. Preferably, the optical polarizer is a polarizing beam splitting prism. Preferably, the polarization beam splitting prism may be a glantrier prism, a wollaston prism or a rochon prism.
In yet another aspect of the present invention, there is provided a beam displacer including the crystalline material described above.
In yet another aspect of the present invention, there is provided a circulator comprising the crystalline material described above.
In still another aspect of the present invention, there is provided an optical isolator comprising the above-described crystalline material.
In yet another aspect of the present invention, there is provided an optical modulator comprising the crystalline material described above.
The invention has the beneficial effects that:
(1) the invention provides a birefringent crystal material A2B(H2C3N3O3)4·4H2O (A ═ K or Rb; B ═ Mg or Ca), first principle calculations show that the crystal has a large birefringence: the birefringence at 800nm is about 0.3.
(2) The invention provides a birefringent crystal material A2B(H2C3N3O3)4·4H2O has 85% transmittance in the spectral range of 200-2500nm and has high transmittance.
(3) The invention also provides a birefringent crystal material A2B(H2C3N3O3)4·4H2O preparation method, adopting water solution method, and growing to obtain colorless transparent A2B(H2C3N3O3)4·4H2And (4) O crystals. The method has simple process, and can obtain high-purity and high-crystallinity A2B(H2C3N3O3)4·4H2And O crystal material.
The crystal material has higher birefringence and high transmittance, is a birefringent crystal material with great potential application value, can be used for manufacturing polarizing prisms, electro-optical adjusting switches and the like, and can be applied to the aspects of optical communication, micro-processing, photoetching and the like.
Drawings
FIG. 1 shows A obtained in examples 1 to 32B(H2C3N3O3)4·4H2Structural schematic diagram of O crystal:
(a) k from example 12Ca(H2C3N3O3)4·4H2A structural schematic diagram of O crystals;
(b) k obtained in example 22Mg(H2C3N3O3)4·4H2A structural schematic diagram of O crystals;
(c) rb from example 32Ca(H2C3N3O3)4·4H2And the structure of the O crystal is shown schematically.
FIG. 2 shows A obtained in examples 1 to 32B(H2C3N3O3)4·4H2XRD pattern of O crystal:
(a) k from example 12Ca(H2C3N3O3)4·4H2An XRD spectrum of the O crystal;
(b) k obtained in example 22Mg(H2C3N3O3)4·4H2An XRD spectrum of the O crystal;
(c) rb from example 32Ca(H2C3N3O3)4·4H2XRD pattern of O crystal.
Fig. 3 is a schematic diagram of a polarization beam splitter-wollaston prism fabricated in example 14.
FIG. 4 is a schematic view of a polarizing prism produced in example 15.
Detailed Description
The crystalline material of the present invention, its preparation and use are described in further detail below with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
Preparation of A by aqueous solution method2B(H2C3N3O3)4·4H2A method of forming a birefringent crystal of O (A ═ K; B ═ Ca) comprising the steps of:
1) dissolving 0.2mmol of potassium carbonate, 0.2mmol of calcium carbonate and 0.4mmol of cyanuric acid in 100mL of water;
2) placing the beaker filled with the mixed aqueous solution obtained in the step 1) on a magnetic stirrer, heating to 100 ℃ and continuously stirring in the heating process until the solution is heated and concentrated to 90mL, and then cooling for crystallization, wherein a large amount of colorless transparent single crystals appear after three days.
3) Washing the crystal obtained in the step 2) with cold water, placing the crystal into a dryer to naturally volatilize water, and testing the obtained crystal by XRD, wherein an X-ray diffraction pattern of the product obtained by the preparation method of the embodiment is shown in a figure 2 (a).
K obtained in this example2Ca(H2C3N3O3)4·4H2The crystal structure of the O birefringent crystal is shown in FIG. 1(a), and the crystal structure diagram is a projection along the c-axis direction, and every two adjacent [ H ] s2C3N3O3]-The groups are connected through hydrogen bonds (H-N … H), and potassium ions and calcium ions are filled in [ H ]2C3N3O3]-The groups form a band-shaped structure.
Calculation from the first principle shows that the crystal of the present embodiment has a large birefringence: the birefringence at 800nm was 0.376.
The transmittance of the crystal material obtained in the embodiment is more than 85% in the spectral range of 200-2500 nm.
The ultraviolet absorption cutoff wavelength of the crystalline material obtained in this example was 231 nm.
Example 2
Preparation of A by aqueous solution method2B(H2C3N3O3)4·4H2A method of forming a birefringent crystal of O (A ═ K; B ═ Mg), comprising the steps of:
1) dissolving 0.2mmol of potassium carbonate, 0.2mmol of magnesium carbonate and 0.4mmol of cyanuric acid in 100mL of water;
2) placing the beaker filled with the mixed aqueous solution obtained in the step 1) on a magnetic stirrer, heating to 100 ℃ and continuously stirring in the heating process until the solution is heated and concentrated to 80mL, and then cooling for crystallization, wherein a large amount of colorless transparent single crystals appear after three days.
3) Washing the crystal obtained in the step 2) with cold water, placing the crystal into a dryer to naturally volatilize water, and testing the obtained crystal by XRD, wherein an X-ray diffraction pattern of the product obtained by the preparation method of the embodiment is shown in a figure 2 (b).
K obtained in this example2Mg(H2C3N3O3)4·4H2The crystal structure of the O birefringent crystal is shown in FIG. 1(b), and the crystal structure diagram is a projection along the c-axis direction, and every two adjacent [ H ] s2C3N3O3]-The groups are connected through hydrogen bonds (H-N … H), and potassium ions and magnesium ions are filled in [ H ]2C3N3O3]-The groups form a band-shaped structure.
Calculation from the first principle shows that the crystal of the present embodiment has a large birefringence: the birefringence at 800nm was 0.376.
The transmittance of the crystal material obtained in the embodiment is more than 85% in the spectral range of 200-2500 nm.
The ultraviolet absorption cut-off wavelength of the crystal material obtained in this example was 235 nm.
Example 3
Preparation of A by aqueous solution method2B(H2C3N3O3)4·4H2A method of forming a birefringent crystal of O (A ═ Rb; B ═ Ca) comprising the steps of:
1) dissolving 0.4mmol of rubidium carbonate, 0.2mmol of calcium carbonate and 0.4mmol of cyanuric acid in 100mL of water;
2) placing the beaker filled with the mixed aqueous solution obtained in the step 1) on a magnetic stirrer, heating to 100 ℃ and continuously stirring in the heating process until the solution is heated and concentrated to 80mL, and then cooling for crystallization, wherein a large amount of colorless transparent single crystals appear after three days.
3) Washing the crystal obtained in the step 2) with cold water, placing the crystal into a dryer to naturally volatilize water, and testing the obtained crystal by XRD, wherein an X-ray diffraction pattern of the product obtained by the preparation method of the embodiment is shown in fig. 2 (c).
Rb obtained in this example2Ca(H2C3N3O3)4·4H2The crystal structure of the O birefringent crystal is shown in FIG. 1(c), and the crystal structure diagram is a projection along the c-axis direction, and every two adjacent [ H ] s2C3N3O3]-The groups are connected through hydrogen bonds (H-N … H), and rubidium ions and magnesium ions are filled in [ H ]2C3N3O3]-The groups form a band-shaped structure.
Calculation from the first principle shows that the crystal of the present embodiment has a large birefringence: the birefringence at 800nm was 0.362.
The transmittance of the crystal material obtained in the embodiment is more than 85% in the spectral range of 200-2500 nm.
The ultraviolet absorption cut-off wavelength of the crystal material obtained in the example is 236 nm.
Example 4
Preparation of A by aqueous solution method2B(H2C3N3O3)4·4H2A method of forming a birefringent crystal of O (A ═ K; B ═ Ca) comprising the steps of:
1) dissolving 0.4mmol of potassium carbonate, 0.2mmol of calcium carbonate and 0.8mmol of cyanuric acid in 100mL of water;
2) placing the beaker filled with the mixed aqueous solution obtained in the step 1) on a magnetic stirrer, heating to 90 ℃ and continuously stirring in the heating process until the solution is heated and concentrated to 80mL, and then cooling for crystallization, wherein a large amount of colorless transparent single crystals appear after three days.
3) Washing the crystal obtained in the step 2) with cold water, then putting the crystal into a dryer to naturally volatilize water, obtaining a birefringent crystal, and carrying out XRD test, wherein the X-ray diffraction pattern of the product obtained by the preparation method of the embodiment is the same as that of the product in the figure 2 (a).
Example 5
Preparation of A by aqueous solution method2B(H2C3N3O3)4·4H2A method of forming a birefringent crystal of O (A ═ K; B ═ Mg), comprising the steps of:
1) dissolving 0.4mmol of potassium carbonate, 0.2mmol of magnesium carbonate and 1mmol of cyanuric acid in 100mL of water;
2) placing the beaker filled with the mixed aqueous solution obtained in the step 1) on a magnetic stirrer, heating to 90 ℃ and continuously stirring in the heating process until the solution is heated and concentrated to 80mL, and then cooling for crystallization, wherein a large amount of colorless transparent single crystals appear after three days.
3) Washing the crystal obtained in the step 2) with cold water, then placing the crystal into a dryer to naturally volatilize moisture, and testing the obtained birefringent crystal by XRD, wherein the X-ray diffraction pattern of the product obtained by the preparation method of the embodiment is the same as that of the product in the figure 2 (b).
Example 6
Preparation of A by aqueous solution method2B(H2C3N3O3)4·4H2A method of forming a birefringent crystal of O (A ═ Rb; B ═ Ca) comprising the steps of:
1) dissolving 0.4mmol of rubidium carbonate, 0.2mmol of calcium carbonate and 1mmol of cyanuric acid in 80mL of water;
2) placing the beaker filled with the mixed aqueous solution obtained in the step 1) on a magnetic stirrer, heating to 90 ℃ and continuously stirring in the heating process until the solution is heated and concentrated to 60mL, then cooling and crystallizing, and a large amount of colorless transparent single crystals appear after three days.
3) Washing the crystal obtained in the step 2) with cold water, then placing the crystal into a dryer to naturally volatilize moisture, and testing the obtained birefringent crystal by XRD, wherein the X-ray diffraction pattern of the product obtained by the preparation method of the embodiment is the same as that of the product in the figure 2 (c).
Example 7
Preparation of A by aqueous solution method2B(H2C3N3O3)4·4H2A method of forming a birefringent crystal of O (A ═ K; B ═ Ca) comprising the steps of:
1) dissolving 0.4mmol of potassium carbonate, 0.2mmol of calcium hydroxide and 1mmol of cyanuric acid in 80mL of water;
2) placing the beaker filled with the mixed aqueous solution obtained in the step 1) on a magnetic stirrer, heating to 80 ℃ and continuously stirring in the heating process until the solution is heated and concentrated to 50mL, and then cooling for crystallization, wherein a large amount of colorless transparent single crystals appear after three days.
3) Washing the crystal obtained in the step 2) with cold water, then placing the crystal into a dryer to naturally volatilize moisture, and testing the obtained birefringent crystal by XRD, wherein the X-ray diffraction pattern of the product obtained by the preparation method of the embodiment is the same as that of the product in the figure 2 (a).
Example 8
Preparation of A by aqueous solution method2B(H2C3N3O3)4·4H2A method of forming a birefringent crystal of O (A ═ K; B ═ Mg), comprising the steps of:
1) dissolving 0.4mmol of potassium carbonate, 0.2mmol of magnesium hydroxide and 1.2mmol of cyanuric acid in 80mL of water;
2) placing the beaker filled with the mixed aqueous solution obtained in the step 1) on a magnetic stirrer, heating to 80 ℃ and continuously stirring in the heating process until the solution is heated and concentrated to 60mL, then cooling and crystallizing, and a large amount of colorless transparent single crystals appear after three days.
3) Washing the crystal obtained in the step 2) with cold water, then placing the crystal into a dryer to naturally volatilize moisture, and testing the obtained birefringent crystal by XRD, wherein the X-ray diffraction pattern of the product obtained by the preparation method of the embodiment is the same as that of the product in the figure 2 (b).
Example 9
Preparation of A by aqueous solution method2B(H2C3N3O3)4·4H2A method of forming a birefringent crystal of O (A ═ Rb; B ═ Ca) comprising the steps of:
1) dissolving 0.4mmol of rubidium carbonate, 0.2mmol of calcium hydroxide and 1.2mmol of cyanuric acid in 70mL of water;
2) the beaker containing the mixed aqueous solution of step 1) was placed on a magnetic stirrer and heated to 80 ℃ with stirring until the solution was concentrated to 60mL by heating, followed by cooling for crystallization, and a large amount of colorless transparent single crystals appeared after three days.
3) Washing the crystal obtained in the step 2) with cold water, then placing the crystal into a dryer to naturally volatilize moisture, and testing the obtained birefringent crystal by XRD, wherein the X-ray diffraction pattern of the product obtained by the preparation method of the embodiment is the same as that of the product in the figure 2 (c).
Example 10
Preparation of A by aqueous solution method2B(H2C3N3O3)4·4H2A method of forming a birefringent crystal of O (A ═ K; B ═ Ca) comprising the steps of:
1) dissolving 0.4mmol of potassium hydroxide, 0.2mmol of calcium hydroxide and 0.8mmol of cyanuric acid in 70mL of water;
2) placing the beaker filled with the mixed aqueous solution obtained in the step 1) on a magnetic stirrer, heating to 80 ℃ and continuously stirring in the heating process until the solution is heated and concentrated to 60mL, then cooling and crystallizing, and a large amount of colorless transparent single crystals appear after three days.
3) Washing the crystal obtained in the step 2) with cold water, then placing the crystal into a dryer to naturally volatilize moisture, and testing the obtained birefringent crystal by XRD, wherein the X-ray diffraction pattern of the product obtained by the preparation method of the embodiment is the same as that of the product in the figure 2 (a).
Example 11
Preparation of A by aqueous solution method2B(H2C3N3O3)4·4H2A method of forming a birefringent crystal of O (A ═ K; B ═ Mg), comprising the steps of:
1) dissolving 0.4mmol of potassium hydroxide, 0.2mmol of magnesium hydroxide and 0.8mmol of cyanuric acid in 60mL of water;
2) the beaker containing the mixed aqueous solution of the step 1) was placed on a magnetic stirrer and heated to 80 ℃ with continuous heating and stirring until the solution was concentrated to 50mL by heating, followed by cooling for crystallization, and a large amount of colorless transparent single crystals appeared after three days.
3) Washing the crystal obtained in the step 2) with cold water, then placing the crystal into a dryer to naturally volatilize moisture, and testing the obtained birefringent crystal by XRD, wherein the X-ray diffraction pattern of the product obtained by the preparation method of the embodiment is the same as that of the product in the figure 2 (b).
Example 12
Preparation of A by aqueous solution method2B(H2C3N3O3)4·4H2A method of forming a birefringent crystal of O (A ═ Rb; B ═ Ca) comprising the steps of:
1) dissolving 0.4mmol of rubidium carbonate, 0.2mmol of calcium hydroxide and 0.8mmol of cyanuric acid in 60mL of water;
2) placing the beaker filled with the mixed aqueous solution obtained in the step 1) on a magnetic stirrer, heating to 80 ℃ and continuously stirring in the heating process until the solution is heated and concentrated to 40mL, and then cooling for crystallization, wherein a large amount of colorless transparent single crystals appear after three days.
3) Washing the crystal obtained in the step 2) with cold water, then placing the crystal into a dryer to naturally volatilize moisture, and testing the obtained birefringent crystal by XRD, wherein the X-ray diffraction pattern of the product obtained by the preparation method of the embodiment is the same as that of the product in the figure 2 (c).
Example 13 Wollaston prism
As shown in FIG. 3, two pieces of K having optical axes perpendicular to each other using example 1 were processed2Ca(H2C3N3O3)4·4H2The prism made of O crystal material is bonded to form a polarization beam splitting prism, and when a light beam is vertically incident to the end face of the prism, the O light and the e light in the prism 1 travel along the same direction at different speeds; when light enters the prism 2 from the prism 1, the optical axis rotates by 90 degrees, and then o light becomes e light and is transmitted by deviating from the normal; the e-light becomes o-light, traveling close to normal. After entering air, the two beams of light are transmitted to the light-thinning medium from the optically dense medium, so that two beams of linearly polarized light which are further separated can be obtained.
EXAMPLE 14 polarizing prism
Two of the K obtained in example 2 were combined2Mg(H2C3N3O3)4·4H2After the O crystals are processed, they are bonded (or air-gap) with canadian gum to make polarizing prisms as shown in fig. 4. When a beam of light is incident perpendicular to the end face of the prism, no deflection occurs to the light o and the light e in the first prism; glue onThe light on the combining surface o is totally reflected and absorbed by the absorbing coating on the right-angle surface of the prism, and the light on the e is emitted from the second prism without deflection.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (28)
1. A crystalline material of formula A2B(H2C3N3O3)4·4H2O, wherein A is selected from K, and B is selected from Mg or Ca; or A is Rb and B is Ca;
the crystal material belongs to a monoclinic system, and the space group is C2/m.
2. The crystalline material of claim 1, wherein the crystalline material is K2Mg(H2C3N3O3)4·4H2O, the unit cell parameters of which are:
α＝γ＝90°，β＝116.876°。
3. the crystalline material of claim 2, wherein K is2Mg(H2C3N3O3)4·4H2The O crystal material has a crystal structure as shown in fig. 1 (b).
4. The crystalline material of claim 2, wherein K is2Mg(H2C3N3O3)4·4H2The O crystal material has an XRD spectrum as shown in fig. 2 (b).
5. The crystalline material of claim 1, wherein the crystalline material is characterized byIs K2Ca(H2C3N3O3)4·4H2O, the unit cell parameters of which are:
α＝γ＝90°，β＝99.574°。
6. the crystalline material of claim 5, wherein K is2Ca(H2C3N3O3)4·4H2The O crystal material has a crystal structure as shown in fig. 1 (a).
7. The crystalline material of claim 5, wherein K is2Ca(H2C3N3O3)4·4H2The O crystal material has an XRD spectrum as shown in figure 2 (a).
8. The crystalline material of claim 1, wherein the crystalline material is Rb2Ca(H2C3N3O3)4·4H2O, the unit cell parameters are:
α＝γ＝90°，β＝99.950°。
9. the crystalline material of claim 8, wherein Rb is2Ca(H2C3N3O3)4·4H2The O crystal material has a crystal structure as shown in fig. 1 (c).
10. The crystalline material of claim 8, wherein Rb is2Ca(H2C3N3O3)4·4H2The O crystal material has an XRD spectrum as shown in figure 2 (c).
11. Crystalline material according to any of claims 1 to 10, characterised in that it has a crystal structure in which every two adjacent [ H ] s2C3N3O3]-The groups are connected through hydrogen bonds (H-N … H), and A ions and B ions are filled in [ H ]2C3N3O3]-The groups form a band-shaped structure.
12. The crystalline material of any of claims 1-10, wherein said crystalline material has a birefringence of 0.3-0.4 at 800 nm.
13. The crystalline material as claimed in any one of claims 1 to 10, wherein the crystalline material has a transmittance of greater than 85% in the spectral range of 200 and 2500 nm.
14. The crystalline material as claimed in any one of claims 1 to 10, wherein the ultraviolet absorption cut-off wavelength of the crystalline material is 230-240 nm.
15. A crystalline material according to any one of claims 1 to 10, characterised in that it is a colourless and transparent crystal.
16. A method for the preparation of a crystalline material as claimed in any one of claims 1 to 15, characterized in that the method comprises the steps of: adopting an aqueous solution method to prepare a compound containing a potassium element and a compound containing a calcium element or a magnesium element; or a compound containing rubidium element and a compound containing calcium element;
mixing with cyanuric acid and water, heating, and cooling for crystallization to obtain the crystal material.
17. The method according to claim 16, wherein the molar volume ratio of the potassium element, the calcium element or the magnesium element, the cyanuric acid to the water is (0.1-20) mmol, (0.3-50) mmol, (0.2-90) mmol, (5-100) mL;
the molar volume ratio of the rubidium element, the calcium element, the cyanuric acid and the water is (0.1-20) mmol, (0.3-50) mmol, (0.2-90) mmol, (5-100) mL.
18. The method of claim 16, wherein the heating temperature is 40 to 100 ℃.
19. The method of claim 16 or 18, wherein the heating is to an extent of: until the volume of the mixed solution is reduced to 45-95% of the initial volume of the mixed solution.
20. The method according to claim 16, wherein the potassium element-containing compound is at least one selected from the group consisting of potassium nitrate, potassium chloride, potassium oxide, potassium fluoride, potassium iodide, potassium carbonate, potassium hydroxide, and potassium fluoroborate.
21. The production method according to claim 16, wherein the rubidium element-containing compound is at least one selected from the group consisting of rubidium nitrate, rubidium chloride, rubidium oxide, rubidium fluoride, rubidium iodide, rubidium carbonate, rubidium hydroxide, and rubidium fluoroborate.
22. The method according to claim 16, wherein the calcium element-containing compound is at least one selected from the group consisting of calcium nitrate, calcium chloride, calcium oxide, calcium fluoride, calcium iodide, calcium carbonate, calcium hydroxide, and calcium fluoroborate.
23. The method according to claim 16, wherein the elemental magnesium-containing compound is at least one selected from the group consisting of magnesium nitrate, magnesium chloride, magnesium oxide, magnesium fluoride, magnesium iodide, magnesium carbonate, magnesium hydroxide, and magnesium fluoroborate.
24. Use of a crystalline material as claimed in any one of claims 1 to 15 as a birefringent crystalline material.
25. Use of the crystalline material of any one of claims 1-15 in an optical device; the optical device is an optical polarizer, a beam shifter, a circulator, an optical isolator or an optical modulator.
26. An optical polarizer comprising the crystalline material of any one of claims 1 to 15.
27. The optical polarizer of claim 26, wherein the optical polarizer is a polarizing beam splitting prism.
28. The optical polarizer according to claim 27, wherein said polarizing beam splitting prism is a glantrier prism, a wollaston prism or a rochon prism.
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