CN111945228A - Birefringent crystal material, preparation method and application thereof - Google Patents
Birefringent crystal material, preparation method and application thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 162
- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002178 crystalline material Substances 0.000 claims abstract description 27
- 230000003287 optical effect Effects 0.000 claims abstract description 20
- 238000002834 transmittance Methods 0.000 claims abstract description 12
- 238000010521 absorption reaction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000011575 calcium Substances 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 27
- 239000011777 magnesium Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 20
- 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 16
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 229910052701 rubidium Inorganic materials 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
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-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
- 230000003595 spectral effect Effects 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
- 239000011259 mixed solution Substances 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 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
- 230000010287 polarization Effects 0.000 claims description 3
- 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
- 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
- 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
- 238000001228 spectrum Methods 0.000 claims 3
- 238000001816 cooling Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- 238000004891 communication Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000001259 photo etching Methods 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 11
- 238000010586 diagram Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- QWVYNEUUYROOSZ-UHFFFAOYSA-N trioxido(oxo)vanadium;yttrium(3+) Chemical compound [Y+3].[O-][V]([O-])([O-])=O QWVYNEUUYROOSZ-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 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
- 229910052791 calcium Inorganic materials 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
- 238000011161 development Methods 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 238000001459 lithography Methods 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
- 229910001419 rubidium ion Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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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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- Crystallography & Structural Chemistry (AREA)
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- 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
Description
技术领域technical field
本发明属于晶体材料领域，具体涉及一种双折射晶体、其制备方法和用途。The invention belongs to the field of crystal materials, in particular to a birefringent crystal, a preparation method and uses thereof.
背景技术Background technique
当一束光投射到晶体界面上一般会产生两束折射光束，这种现象叫做双折射，产生双折射现象的主要原因是由于晶体材料的各向异性，这两束折射光线的夹角大小与它们的传播方向和偏振状态有关，能够产生双折射现象的晶体叫双折射晶体，双折射晶体的作用类似于两个透振方向相互垂直的起偏器。双折射是判断电光功能晶体材料的重要光学性能指标。利用双折射晶体可以得到线偏振光，目前线偏振光在光学领域中的应用非常广泛，例如光刻、通讯、微加工等领域，目前国内外的双折射晶体有成千上万种，但是能够真正实现制作偏振器件的双折射晶体不多，这主要是由于偏光棱镜对双折射晶体要求比较严格，一般需要满足几个要求：(1)晶体的结构最好为单轴晶；(2)在使用波段内晶体具有较大的双折射率；(3)无光学级要求的缺陷，即无包裹体、裂缝等；(4)容易生长并获得大尺寸的单晶；(5)物化性能稳定；(6)不容易潮解；(7)抗激光损伤阈值高。When a beam of light is projected on the crystal interface, two beams of refracted beams are generally generated. This phenomenon is called birefringence. The main reason for the phenomenon of birefringence is due to the anisotropy of the crystal material. The angle between the two beams of refracted beams is different from Their propagation direction is related to the polarization state. The crystals that can produce birefringence are called birefringent crystals. The function of birefringent crystals is similar to that of two polarizers whose transmission directions are perpendicular to each other. Birefringence is an important optical performance index for judging electro-optical functional crystal materials. Linearly polarized light can be obtained by using birefringent crystals. At present, linearly polarized light is widely used in the field of optics, such as lithography, communications, micromachining and other fields. At present, there are thousands of birefringent crystals at home and abroad, but they can There are not many birefringent crystals that can actually make polarizing devices. This is mainly because polarizing prisms have strict requirements on birefringent crystals, and generally need to meet several requirements: (1) the structure of the crystal is preferably uniaxial; (2) in the The crystal in the use band has a large birefringence; (3) there are no defects required by the optical level, that is, no inclusions, cracks, etc.; (4) it is easy to grow and obtain large-sized single crystals; (5) The physical and chemical properties are stable; (6) It is not easy to deliquescence; (7) The anti-laser damage threshold is high.
目前已经商业化的双折射晶体有冰洲石、铌酸锂、钒酸钇、金红石、氟化镁和高温相偏硼酸钡等。对于冰洲石来说，它具有较宽的透过范围和较大的折射率，但是制作工艺复杂，人工生长困难，无法得到大尺寸的单晶，另外冰洲石在350nm以下存在严重的吸收，其偏振器件无法应用在紫外深紫外区域，只能应用在可见和红外波段。对于钒酸钇晶体来说，在低于400nm的紫外波段它的透过能力很差，因此无法在紫外深紫外波段应用，另外钒酸钇晶体在可见波段激光损伤阈值低，所以该晶体仅能应用于中红外波段。氟化镁晶体属于四方晶系，它的透过范围很宽，范围是110nm-8500nm，是唯一能够用于紫外深紫外波段的双折射晶体，但是它有一个严重的缺陷就是它的双折射率比较小，所以如果用氟化镁晶体做偏振器件会存在体积过大的缺点。同样受折射率困扰的还有二氧化硅晶体，所以它们都不适合做偏振器件。而对于高温相偏硼酸钡来说，它具有较宽的光谱透过范围(189-3500nm)，较短的紫外截止边(189nm)，较大的双折射率(0.159@253.7nm)，高的激光损伤阈值，在紫外区具有重要的应用价值。但是该晶体在193nm的透过率低于40％。且该晶体在高温下存在相变，生长过程中容易开裂，这些缺点都影响了晶体的应用。Currently commercialized birefringent crystals include icelandite, lithium niobate, yttrium vanadate, rutile, magnesium fluoride, and high-temperature phase barium metaborate. For Bingzhou stone, it has a wide transmission range and a larger refractive index, but the production process is complicated, artificial growth is difficult, and large-sized single crystals cannot be obtained. In addition, Bingzhou stone has serious absorption below 350 nm. , its polarizing device cannot be used in the ultraviolet and deep ultraviolet region, but can only be used in the visible and infrared bands. For yttrium vanadate crystal, its transmission ability is very poor in the ultraviolet band below 400nm, so it cannot be applied in the ultraviolet and deep ultraviolet band. In addition, the yttrium vanadate crystal has a low laser damage threshold in the visible band, so the crystal can only Applied to the mid-infrared band. Magnesium fluoride crystal belongs to the tetragonal crystal system. Its transmission range is very wide, ranging from 110nm to 8500nm. It is the only birefringent crystal that can be used in the ultraviolet and deep ultraviolet bands. However, it has a serious defect that is its birefringence. It is relatively small, so if a magnesium fluoride crystal is used as a polarizing device, there will be the disadvantage of being too bulky. Also troubled by the refractive index are silicon dioxide crystals, so they are not suitable for polarizers. For high-temperature phase barium metaborate, it has a wider spectral transmission range (189-3500nm), a shorter UV cut-off edge (189nm), a larger birefringence (0.159@253.7nm), a high The laser damage threshold has important application value in the ultraviolet region. However, the transmittance of this crystal at 193 nm is lower than 40%. In addition, the crystal has a phase transition at high temperature and is easy to crack during the growth process. These shortcomings all affect the application of the crystal.
随着科技的发展，人们对双折射晶体的要求也越来越高，不论是从质还是从量上，所以寻找一种优秀的双折射晶体具有十分重要的意义。而优秀的双折射晶体又要求其易于加工和生长，且其具有较大的双折射率和透过性能，再加上物化性能稳定，所以科研工作者近年来一直在不断地探索和尝试中，致力于寻找到一种优秀的双折射晶体材料并用于实际应用中。With the development of science and technology, people's requirements for birefringent crystals are getting higher and higher, both in terms of quality and quantity, so it is of great significance to find an excellent birefringent crystal. And excellent birefringent crystals are required to be easy to process and grow, and have large birefringence and transmittance properties, coupled with stable physical and chemical properties, so researchers have been exploring and trying in recent years Dedicated to finding an excellent birefringent crystal material and using it in practical applications.
发明内容SUMMARY OF THE INVENTION
本发明的一个方面，提供一种晶体材料，其化学式以A2B(H2C3N3O3)4·4H2O来表示，其中，A选自K和/或Rb；B选自Mg和/或Ca；One aspect of the present invention provides a crystalline material whose chemical formula is represented by A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O, wherein A is selected from K and/or Rb; B is selected from Mg and/or Ca;
所述的晶体材料属于单斜晶系，空间群是C2/m。The crystalline material belongs to the monoclinic system, and the space group is C2/m.
根据本发明示例性的技术方案，所述晶体材料为K2Mg(H2C3N3O3)4·4H2O，其单胞参数为：
根据本发明示例性的技术方案，所述晶体材料为K2Ca(H2C3N3O3)4·4H2O，其单胞参数为：
根据本发明示例性的技术方案，所述晶体材料为Rb2Ca(H2C3N3O3)4·4H2O，其晶胞参数为：
根据本发明的晶体材料，其晶体结构中每两个相邻的[H2C3N3O3]-基团之间通过氢键(H-N…H)连接，A离子和B离子填充在[H2C3N3O3]-基团组成的带状结构之间。According to the crystal material of the present invention, every two adjacent [H 2 C 3 N 3 O 3 ] -groups in the crystal structure are connected by hydrogen bonds (HN...H), and A ions and B ions are filled in [ H 2 C 3 N 3 O 3 ] -groups between the band-like structures.
根据本发明的晶体材料，所述晶体材料在800nm下双折射率为0.3-0.4，例如0.35-0.4，作为示例，双折射率为0.362、0.376。According to the crystalline material of the present invention, the birefringence of the crystalline material at 800 nm is 0.3-0.4, for example, 0.35-0.4, as an example, the birefringence is 0.362, 0.376.
根据本发明的晶体材料，所述晶体材料在200-2500nm光谱范围内透过率大于85％，具有高的透过率。According to the crystal material of the present invention, the transmittance of the crystal material in the spectral range of 200-2500 nm is greater than 85%, and has high transmittance.
根据本发明的晶体材料，所述晶体材料的紫外吸收截止波长为237nm左右，例如为230-240nm，作为示例，紫外吸收截止波长为231nm、235nm或236nm。According to the crystal material of the present invention, the ultraviolet absorption cut-off wavelength of the crystal material is about 237 nm, for example, 230-240 nm. As an example, the ultraviolet absorption cut-off wavelength is 231 nm, 235 nm or 236 nm.
根据本发明的晶体材料，所述晶体材料为无色透明的晶体。According to the crystal material of the present invention, the crystal material is a colorless and transparent crystal.
本发明的又一方面，提供所述晶体材料的制备方法，该制备方法包括如下步骤：采用水溶液法，将含有钾元素和/或铷元素的化合物、含有钙元素和/或镁元素的化合物、氰尿酸和水混合后加热，之后冷却结晶，得到所述晶体材料。Another aspect of the present invention provides a method for preparing the crystalline material, the preparation method comprising the steps of: using an aqueous solution method to combine a compound containing potassium element and/or rubidium element, a compound containing calcium element and/or magnesium element, The cyanuric acid and water are mixed and heated, and then cooled and crystallized to obtain the crystalline material.
根据本发明的制备方法，所述钾元素和/或铷元素、钙元素和/或镁元素、氰尿酸与水的摩尔体积比为(0.1-20)mmol:(0.3-50)mmol:(0.2-90)mmol:(5-100)mL。优选地，所述摩尔体积比为(0.1-10)mmol:(0.3-30)mmol:(0.2-80)mmol:(5-80)mL，更优选为(0.1-1)mmol:(0.3-1)mmol:(0.2-2)mmol:(5-80)mL。示例性地，所述摩尔体积比为0.2mmol:0.2mmol:0.4mmol:100mL、0.4mmol:0.2mmol:0.4mmol:100mL、0.4mmol:0.2mmol:0.8mmol:100mL、0.4mmol:0.2mmol:1mmol:100mL、0.4mmol:0.2mmol:1mmol:80mL、0.4mmol:0.2mmol:1.2mmol:80mL、0.4mmol:0.2mmol:1.2mmol:70mL、0.4mmol:0.2mmol:0.8mmol:70mL、0.4mmol:0.2mmol:0.8mmol:60mL。According to the preparation method of the present invention, the molar volume ratio of the potassium element and/or rubidium element, calcium element and/or magnesium element, cyanuric acid and water is (0.1-20) mmol: (0.3-50) mmol: (0.2 -90) mmol: (5-100) mL. Preferably, the molar volume ratio is (0.1-10) mmol: (0.3-30) mmol: (0.2-80) mmol: (5-80) mL, more preferably (0.1-1) mmol: (0.3- 1) mmol: (0.2-2) mmol: (5-80) mL. Exemplarily, the molar volume ratio is 0.2mmol:0.2mmol:0.4mmol:100mL, 0.4mmol:0.2mmol:0.4mmol:100mL, 0.4mmol:0.2mmol:0.8mmol:100mL, 0.4mmol:0.2mmol:1mmol : 100mL, 0.4mmol: 0.2mmol: 1mmol: 80mL, 0.4mmol: 0.2mmol: 1.2mmol: 80mL, 0.4mmol: 0.2mmol: 1.2mmol: 70mL, 0.4mmol: 0.2mmol: 0.8mmol: 70mL, 0.4mmol: 0.2 mmol: 0.8 mmol: 60 mL.
根据本发明的制备方法，所述加热的温度为40-100℃，例如温度为60-100℃；示例性地，温度可以为65℃、70℃、75℃、80℃、85℃、90℃、100℃。优选地，所述加热的程度为：至混合液的体积减少为混合液初始体积的45-95％为止，例如50-90％，示例性地，所述加热至混合液的体积减少为混合液初始体积的50％、60％、70％、80％或90％为止。According to the preparation method of the present invention, the heating temperature is 40-100°C, for example, the temperature is 60-100°C; exemplarily, the temperature can be 65°C, 70°C, 75°C, 80°C, 85°C, 90°C , 100℃. Preferably, the degree of heating is as follows: until the volume of the mixed solution is reduced to 45-95% of the initial volume of the mixed solution, such as 50-90%, exemplarily, the heating is performed until the volume of the mixed solution is reduced to the mixed solution up to 50%, 60%, 70%, 80% or 90% of the initial volume.
根据本发明的制备方法，所述含钾元素的化合物可以选自硝酸钾、氯化钾、氧化钾、氟化钾、碘化钾、碳酸钾、氢氧化钾和氟硼酸钾等中的至少一种。优选地，所述含钾元素的化合物可以选自硝酸钾、碳酸钾和氢氧化钾中的至少一种。示例性地，所述含钾元素的化合物可以选自硝酸钾、碳酸钾或氢氧化钾。According to the preparation method of the present invention, the potassium element-containing compound can be selected from at least one of potassium nitrate, potassium chloride, potassium oxide, potassium fluoride, potassium iodide, potassium carbonate, potassium hydroxide, potassium fluoroborate, and the like. Preferably, the potassium-containing compound may be selected from at least one of potassium nitrate, potassium carbonate and potassium hydroxide. Exemplarily, the potassium element-containing compound may be selected from potassium nitrate, potassium carbonate or potassium hydroxide.
根据本发明的制备方法，所述含铷元素的化合物可以选自硝酸铷、氯化铷、氧化铷、氟化铷、碘化铷、碳酸铷、氢氧化铷和氟硼酸铷等中的至少一种。优选地，所述含铷元素的化合物可以选自硝酸铷和/或碳酸铷。示例性地，所述含铷元素的化合物可以选自碳酸铷。According to the preparation method of the present invention, the compound containing rubidium element can be selected from at least one of rubidium nitrate, rubidium chloride, rubidium oxide, rubidium fluoride, rubidium iodide, rubidium carbonate, rubidium hydroxide and rubidium fluoroborate, etc. kind. Preferably, the compound containing rubidium element may be selected from rubidium nitrate and/or rubidium carbonate. Exemplarily, the compound containing rubidium element may be selected from rubidium carbonate.
根据本发明的制备方法，所述含钙元素的化合物可以选自硝酸钙、氯化钙、氧化钙、氟化钙、碘化钙、碳酸钙、氢氧化钙和氟硼酸钙等中的至少一种。优选地，所述含钙元素的化合物可以选自硝酸钙、碳酸钙和氢氧化钙中的至少一种。示例性地，所述含钙元素的化合物可以选自碳酸钙或氢氧化钙。According to the preparation method of the present invention, the compound containing calcium element can be selected from at least one of calcium nitrate, calcium chloride, calcium oxide, calcium fluoride, calcium iodide, calcium carbonate, calcium hydroxide and calcium fluoroborate, etc. kind. Preferably, the calcium element-containing compound may be selected from at least one of calcium nitrate, calcium carbonate and calcium hydroxide. Exemplarily, the calcium element-containing compound may be selected from calcium carbonate or calcium hydroxide.
根据本发明的制备方法，所述含镁元素的化合物可以选自硝酸镁、氯化镁、氧化镁、氟化镁、碘化镁、碳酸镁、氢氧化镁和氟硼酸镁等中的至少一种。优选地，所述含镁元素的化合物可以选自硝酸镁、碳酸镁和氢氧化镁中的至少一种。示例性地，所述含镁元素的化合物可以选自碳酸镁或氢氧化镁。According to the preparation method of the present invention, the magnesium element-containing compound can be selected from at least one of magnesium nitrate, magnesium chloride, magnesium oxide, magnesium fluoride, magnesium iodide, magnesium carbonate, magnesium hydroxide and magnesium fluoroborate. Preferably, the magnesium element-containing compound may be selected from at least one of magnesium nitrate, magnesium carbonate and magnesium hydroxide. Exemplarily, the magnesium-containing compound may be selected from magnesium carbonate or magnesium hydroxide.
本发明的又一方面，提供所述晶体材料作为双折射晶体材料的应用。Another aspect of the present invention provides the application of the crystal material as a birefringent crystal material.
本发明的又一方面，提供所述晶体材料在光学器件中的应用。优选地，所述光学器件可以为光学起偏器、光束位移器、环形器、光隔离器或光学调制器。In yet another aspect of the present invention, there is provided an application of the crystal material in an optical device. Preferably, the optical device may be an optical polarizer, a beam shifter, a circulator, an optical isolator or an optical modulator.
本发明的又一方面，提供一种光学起偏器，其包含上述所述晶体材料。优选地，所述光学起偏器为偏振分束棱镜。优选地，所述偏振分束棱镜可以为格兰泰勒棱镜、渥拉斯顿棱镜或洛匈棱镜。In yet another aspect of the present invention, there is provided an optical polarizer comprising the above-mentioned crystalline material. Preferably, the optical polarizer is a polarizing beam splitter prism. Preferably, the polarizing beam splitting prism may be a Glan-Taylor prism, a Wollaston prism or a Rochnian prism.
本发明的又一方面，提供一种光束位移器，其包含上述所述晶体材料。In yet another aspect of the present invention, a beam displacer is provided, which includes the above-mentioned crystal material.
本发明的又一方面，提供一种环形器，其包含上述所述晶体材料。In yet another aspect of the present invention, there is provided a circulator comprising the above-mentioned crystalline material.
本发明的又一方面，提供一种光隔离器，其包含上述所述晶体材料。In yet another aspect of the present invention, an optical isolator is provided, which includes the above-mentioned crystalline material.
本发明的又一方面，提供一种光学调制器，其包含上述所述晶体材料。In yet another aspect of the present invention, there is provided an optical modulator comprising the above-mentioned crystalline material.
本发明的有益效果：Beneficial effects of the present invention:
(1)本发明提供了一种双折射晶体材料A2B(H2C3N3O3)4·4H2O(A＝K或Rb；B＝Mg或Ca)，第一性原理计算显示该晶体具有较大的双折射率：在800nm下的双折射率为0.3左右。(1) The present invention provides a birefringent crystal material A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O (A=K or Rb; B=Mg or Ca), first-principles calculation This crystal is shown to have a large birefringence: around 0.3 at 800 nm.
(2)本发明所提供的双折射晶体材料A2B(H2C3N3O3)4·4H2O在200～2500nm光谱范围具有85％的透过率，透过率高。(2) The birefringent crystal material A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O provided by the present invention has a transmittance of 85% in the spectral range of 200-2500 nm, and the transmittance is high.
(3)本发明还提供了双折射晶体材料A2B(H2C3N3O3)4·4H2O的制备方法，采用水溶液法，生长得到了无色透明的A2B(H2C3N3O3)4·4H2O晶体。该方法过程简单，可得到高纯度、高结晶度的A2B(H2C3N3O3)4·4H2O晶体材料。(3) The present invention also provides a method for preparing the birefringent crystal material A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O. The aqueous solution method is used to grow a colorless and transparent A 2 B(H 2 O) 2 C 3 N 3 O 3 ) 4 ·4H 2 O crystal. The method has a simple process and can obtain A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O crystal material with high purity and high crystallinity.
该晶体材料具有较大的双折射率和高的透过率，为具有极大潜在应用价值的双折射晶体材料，可用于制作偏振棱镜，电光调节开关等，并且在光学通讯、微加工和光刻等方面均可以应用。The crystal material has large birefringence and high transmittance, and is a birefringent crystal material with great potential application value. It can be used to make polarizing prisms, electro-optic adjustment switches, etc. Engraving and so on can be applied.
附图说明Description of drawings
图1是实施例1-3得到的A2B(H2C3N3O3)4·4H2O晶体的结构示意图：Figure 1 is a schematic structural diagram of the A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O crystal obtained in Example 1-3:
(a)实施例1得到的K2Ca(H2C3N3O3)4·4H2O晶体的结构示意图；(a) A schematic structural diagram of the K 2 Ca(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O crystal obtained in Example 1;
(b)实施例2得到的K2Mg(H2C3N3O3)4·4H2O晶体的结构示意图；(b) a schematic structural diagram of the K 2 Mg(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O crystal obtained in Example 2;
(c)实施例3得到的Rb2Ca(H2C3N3O3)4·4H2O晶体的结构示意图。(c) A schematic structural diagram of the Rb 2 Ca(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O crystal obtained in Example 3.
图2是实施例1-3得到的A2B(H2C3N3O3)4·4H2O晶体的XRD图谱：Fig. 2 is the XRD pattern of A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O crystal obtained in Example 1-3:
(a)实施例1得到的K2Ca(H2C3N3O3)4·4H2O晶体的XRD图谱；(a) XRD pattern of K 2 Ca(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O crystal obtained in Example 1;
(b)实施例2得到的K2Mg(H2C3N3O3)4·4H2O晶体的XRD图谱；(b) XRD pattern of K 2 Mg(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O crystal obtained in Example 2;
(c)实施例3得到的Rb2Ca(H2C3N3O3)4·4H2O晶体的XRD图谱。(c) XRD pattern of the Rb 2 Ca(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O crystal obtained in Example 3.
图3是实施例14制作的偏振分束棱镜-渥拉斯顿棱镜的示意图。FIG. 3 is a schematic diagram of the polarizing beam splitter prism-Wollaston prism fabricated in Example 14. FIG.
图4是实施例15制作的偏振棱镜的示意图。FIG. 4 is a schematic diagram of the polarizing prism fabricated in Example 15. FIG.
具体实施方式Detailed ways
下文将结合具体实施例对本发明的晶体材料及其制备方法和应用做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。The crystal material of the present invention and its preparation method and application will be described in further detail below with reference to specific embodiments. It should be understood that the following examples are only for illustrating and explaining the present invention, and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the intended protection scope of the present invention.
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备。Unless otherwise stated, the starting materials and reagents used in the following examples are commercially available or can be prepared by known methods.
实施例1Example 1
水溶液法制备A2B(H2C3N3O3)4·4H2O(A＝K；B＝Ca)双折射晶体的方法，包括如下步骤：The method for preparing A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O (A=K; B=Ca) birefringent crystal by an aqueous solution method comprises the following steps:
1)将0.2mmol碳酸钾，0.2mmol碳酸钙，0.4mmol氰尿酸溶解于100mL水中；1) 0.2mmol potassium carbonate, 0.2mmol calcium carbonate, 0.4mmol cyanuric acid are dissolved in 100mL water;
2)将装有步骤1)混合水溶液的烧杯放在磁力搅拌器上加热至100摄氏度并在加热过程中不断搅拌，直到溶液被加热浓缩到90mL，而后冷却结晶，三天后大量无色的透明单晶出现。2) The beaker containing the mixed aqueous solution in step 1) was heated to 100 degrees Celsius on a magnetic stirrer and stirred continuously during the heating process until the solution was heated and concentrated to 90 mL, and then cooled and crystallized. After three days, a large number of colorless transparent single crystal appears.
3)将步骤2)得到的晶体用冷水洗涤后放入干燥器中自然挥发水分，将得到的晶体进行XRD的测试，本实施例制备方法所得产品的X-射线衍射图谱参照图2(a)所示。3) the crystal obtained in step 2) is washed with cold water and put into a desiccator to naturally volatilize water, and the obtained crystal is carried out to the test of XRD, and the X-ray diffraction pattern of the product obtained by the preparation method of the present embodiment refers to Fig. 2 (a) shown.
本实施例得到的K2Ca(H2C3N3O3)4·4H2O双折射晶体的晶体结构如图1(a)所示，其晶体结构图是沿着c轴方向的投影，每两个相邻的[H2C3N3O3]-基团之间通过氢键(H-N…H)连接，钾离子和钙离子填充在[H2C3N3O3]-基团组成的带状结构之间。The crystal structure of the K 2 Ca(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O birefringent crystal obtained in this example is shown in Figure 1(a), and its crystal structure is a projection along the c-axis direction , every two adjacent [H 2 C 3 N 3 O 3 ] -groups are connected by hydrogen bonds (HN…H), and potassium ions and calcium ions are filled in [H 2 C 3 N 3 O 3 ] - between the band-like structures composed of groups.
由第一性原理计算显示本实施例晶体具有较大的双折射率：在800nm下的双折射率为0.376。The first-principles calculations show that the crystal of this example has a large birefringence: the birefringence at 800 nm is 0.376.
本实施例得到的晶体材料在200-2500nm光谱范围内透过率大于85％。The transmittance of the crystal material obtained in this example is greater than 85% in the spectral range of 200-2500 nm.
本实施例得到的晶体材料的紫外吸收截止波长在231nm。The ultraviolet absorption cut-off wavelength of the crystal material obtained in this example is 231 nm.
实施例2Example 2
水溶液法制备A2B(H2C3N3O3)4·4H2O(A＝K；B＝Mg)双折射晶体的方法，包括如下步骤：The method for preparing A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O (A=K; B=Mg) birefringent crystal by an aqueous solution method comprises the following steps:
1)将0.2mmol碳酸钾，0.2mmol碳酸镁，0.4mmol氰尿酸溶解于100mL水中；1) dissolve 0.2mmol potassium carbonate, 0.2mmol magnesium carbonate, 0.4mmol cyanuric acid in 100mL water;
2)将装有步骤1)混合水溶液的烧杯放在磁力搅拌器上加热至100摄氏度并在加热过程中不断搅拌，直到溶液被加热浓缩到80mL，而后冷却结晶，三天后大量无色的透明单晶出现。2) The beaker containing the mixed aqueous solution in step 1) was heated to 100 degrees Celsius on a magnetic stirrer and stirred continuously during the heating process until the solution was heated and concentrated to 80 mL, and then cooled and crystallized. After three days, a large number of colorless transparent single crystal appears.
3)将步骤2)得到的晶体用冷水洗涤后放入干燥器中自然挥发水分，将得到的晶体进行XRD的测试，本实施例制备方法所得产品的X射线衍射图谱参照图2(b)所示。3) the crystal obtained in step 2) is washed with cold water and put into a desiccator to naturally volatilize water, and the obtained crystal is tested by XRD, the X-ray diffraction pattern of the product obtained by the preparation method of the present embodiment is with reference to Figure 2 (b). Show.
本实施例得到的K2Mg(H2C3N3O3)4·4H2O双折射晶体的晶体结构如图1(b)所示，其晶体结构图是沿着c轴方向的投影，每两个相邻的[H2C3N3O3]-基团之间通过氢键(H-N…H)连接，钾离子和镁离子填充在[H2C3N3O3]-基团组成的带状结构之间。The crystal structure of the K 2 Mg(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O birefringent crystal obtained in this example is shown in Figure 1(b), and the crystal structure is a projection along the c-axis direction , every two adjacent [H 2 C 3 N 3 O 3 ] -groups are connected by hydrogen bonds (HN…H), and potassium ions and magnesium ions are filled in [H 2 C 3 N 3 O 3 ] - between the band-like structures composed of groups.
由第一性原理计算显示本实施例晶体具有较大的双折射率：在800nm下的双折射率为0.376。The first-principles calculations show that the crystal of this example has a large birefringence: the birefringence at 800 nm is 0.376.
本实施例得到的晶体材料在200-2500nm光谱范围内透过率大于85％。The transmittance of the crystal material obtained in this example is greater than 85% in the spectral range of 200-2500 nm.
本实施例得到的晶体材料的紫外吸收截止波长在235nm。The ultraviolet absorption cut-off wavelength of the crystal material obtained in this example is 235 nm.
实施例3Example 3
水溶液法制备A2B(H2C3N3O3)4·4H2O(A＝Rb；B＝Ca)双折射晶体的方法，包括如下步骤：The method for preparing A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O (A=Rb; B=Ca) birefringent crystal by an aqueous solution method comprises the following steps:
1)将0.4mmol碳酸铷，0.2mmol碳酸钙，0.4mmol氰尿酸溶解于100mL水中；1) 0.4mmol rubidium carbonate, 0.2mmol calcium carbonate, 0.4mmol cyanuric acid are dissolved in 100mL water;
2)将装有步骤1)混合水溶液的烧杯放在磁力搅拌器上加热至100摄氏度并在加热过程中不断搅拌，直到溶液被加热浓缩到80mL，而后冷却结晶，三天后大量无色的透明单晶出现。2) The beaker containing the mixed aqueous solution in step 1) was heated to 100 degrees Celsius on a magnetic stirrer and stirred continuously during the heating process until the solution was heated and concentrated to 80 mL, and then cooled and crystallized. After three days, a large number of colorless transparent single crystal appears.
3)将步骤2)得到的晶体用冷水洗涤后放入干燥器中自然挥发水分，将得到的晶体进行XRD的测试，本实施例制备方法所得产品的X射线衍射图谱参照图2(c)所示。3) the crystal obtained in step 2) is washed with cold water and then put into a desiccator to naturally volatilize water, and the obtained crystal is subjected to the test of XRD. The X-ray diffraction pattern of the product obtained by the preparation method of the present embodiment refers to that shown in Figure 2 (c). Show.
本实施例得到的Rb2Ca(H2C3N3O3)4·4H2O双折射晶体的晶体结构如图1(c)所示，其晶体结构图是沿着c轴方向的投影，每两个相邻的[H2C3N3O3]-基团之间通过氢键(H-N…H)连接，铷离子和镁离子填充在[H2C3N3O3]-基团组成的带状结构之间。The crystal structure of the Rb 2 Ca(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O birefringent crystal obtained in this example is shown in Figure 1(c), and its crystal structure is a projection along the c-axis direction , every two adjacent [H 2 C 3 N 3 O 3 ] -groups are connected by hydrogen bonds (HN…H), and rubidium ions and magnesium ions are filled in [H 2 C 3 N 3 O 3 ] - between the band-like structures composed of groups.
由第一性原理计算显示本实施例晶体具有较大的双折射率：在800nm下的双折射率为0.362。The first-principles calculations show that the crystal of this example has a large birefringence: the birefringence at 800 nm is 0.362.
本实施例得到的晶体材料在200-2500nm光谱范围内透过率大于85％。The transmittance of the crystal material obtained in this example is greater than 85% in the spectral range of 200-2500 nm.
本实施例得到的晶体材料的紫外吸收截止波长在236nm。The ultraviolet absorption cut-off wavelength of the crystal material obtained in this example is 236 nm.
实施例4Example 4
水溶液法制备A2B(H2C3N3O3)4·4H2O(A＝K；B＝Ca)双折射晶体的方法，包括如下步骤：The method for preparing A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O (A=K; B=Ca) birefringent crystal by an aqueous solution method comprises the following steps:
1)将0.4mmol碳酸钾，0.2mmol碳酸钙，0.8mmol氰尿酸溶解于100mL水中；1) 0.4mmol potassium carbonate, 0.2mmol calcium carbonate, 0.8mmol cyanuric acid are dissolved in 100mL water;
2)将装有步骤1)混合水溶液的烧杯放在磁力搅拌器上加热至90摄氏度并在加热过程中不断搅拌，直到溶液被加热浓缩到80mL，而后冷却结晶，三天后大量无色的透明单晶出现。2) The beaker containing the mixed aqueous solution in step 1) was heated to 90 degrees Celsius on a magnetic stirrer and stirred continuously during the heating process until the solution was heated and concentrated to 80 mL, and then cooled and crystallized. After three days, a large number of colorless transparent single crystal appears.
3)将步骤2)得到的晶体用冷水洗涤后随后放入干燥器中自然挥发水分，得到双折射晶体进行XRD的测试，本实施例制备方法所得产品的X射线衍射图谱与图2(a)相同。3) the crystal obtained in step 2) is washed with cold water and then put into a desiccator to naturally volatilize water to obtain a birefringent crystal and carry out the test of XRD. same.
实施例5Example 5
水溶液法制备A2B(H2C3N3O3)4·4H2O(A＝K；B＝Mg)双折射晶体的方法，包括如下步骤：The method for preparing A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O (A=K; B=Mg) birefringent crystal by an aqueous solution method comprises the following steps:
1)将0.4mmol碳酸钾，0.2mmol碳酸镁，1mmol氰尿酸溶解于100mL水中；1) 0.4mmol potassium carbonate, 0.2mmol magnesium carbonate, 1mmol cyanuric acid are dissolved in 100mL water;
2)将装有步骤1)混合水溶液的烧杯放在磁力搅拌器上加热至90摄氏度并在加热过程中不断搅拌，直到溶液被加热浓缩到80mL，而后冷却结晶，三天后大量无色的透明单晶出现。2) The beaker containing the mixed aqueous solution in step 1) was heated to 90 degrees Celsius on a magnetic stirrer and stirred continuously during the heating process until the solution was heated and concentrated to 80 mL, and then cooled and crystallized. After three days, a large number of colorless transparent single crystal appears.
3)将步骤2)得到的晶体用冷水洗涤后随后放入干燥器中自然挥发水分，将得到双折射晶体进行XRD的测试，本实施例制备方法所得产品的X射线衍射图谱与图2(b)相同。3) the crystal obtained in step 2) is washed with cold water and then put into the dryer to naturally volatilize moisture, the birefringent crystal will be obtained and carry out the test of XRD. )same.
实施例6Example 6
水溶液法制备A2B(H2C3N3O3)4·4H2O(A＝Rb；B＝Ca)双折射晶体的方法，包括如下步骤：The method for preparing A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O (A=Rb; B=Ca) birefringent crystal by an aqueous solution method comprises the following steps:
1)将0.4mmol碳酸铷，0.2mmol碳酸钙，1mmol氰尿酸溶解于80mL水中；1) 0.4mmol rubidium carbonate, 0.2mmol calcium carbonate, 1mmol cyanuric acid are dissolved in 80mL water;
2)将装有步骤1)混合水溶液的烧杯放在磁力搅拌器上加热至90摄氏度并在加热过程中不断搅拌，直到溶液被加热浓缩到60mL，而后冷却结晶，三天后大量无色的透明单晶出现。2) The beaker containing the mixed aqueous solution in step 1) was heated to 90 degrees Celsius on a magnetic stirrer and stirred continuously during the heating process until the solution was heated and concentrated to 60 mL, and then cooled and crystallized. After three days, a large number of colorless transparent single crystal appears.
3)将步骤2)得到的晶体用冷水洗涤后随后放入干燥器中自然挥发水分，将得到双折射晶体进行XRD的测试，本实施例制备方法所得产品的X射线衍射图谱与图2(c)相同。3) the crystal obtained in step 2) is washed with cold water and then put into the desiccator to naturally volatilize water, the birefringent crystal will be obtained and carry out the test of XRD, the X-ray diffraction pattern of the product obtained by the preparation method of the present embodiment is the same as that of Fig. 2 (c )same.
实施例7Example 7
水溶液法制备A2B(H2C3N3O3)4·4H2O(A＝K；B＝Ca)双折射晶体的方法，包括如下步骤：The method for preparing A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O (A=K; B=Ca) birefringent crystal by an aqueous solution method comprises the following steps:
1)将0.4mmol碳酸钾，0.2mmol氢氧化钙，1mmol氰尿酸溶解于80mL水中；1) 0.4mmol potassium carbonate, 0.2mmol calcium hydroxide, 1mmol cyanuric acid are dissolved in 80mL water;
2)将装有步骤1)混合水溶液的烧杯放在磁力搅拌器上加热至80摄氏度并在加热过程中不断搅拌，直到溶液被加热浓缩到50mL，而后冷却结晶，三天后大量无色的透明单晶出现。2) The beaker containing the mixed aqueous solution in step 1) was heated to 80 degrees Celsius on a magnetic stirrer and stirred continuously during the heating process until the solution was heated and concentrated to 50 mL, and then cooled and crystallized. After three days, a large number of colorless transparent single crystal appears.
3)将步骤2)得到的晶体用冷水洗涤后随后放入干燥器中自然挥发水分，将得到双折射晶体进行XRD的测试，本实施例制备方法所得产品的X射线衍射图谱与图2(a)相同。3) the crystal obtained in step 2) is washed with cold water and then put into the desiccator to naturally volatilize water, the birefringent crystal will be obtained and carry out the test of XRD, the X-ray diffraction pattern of the product obtained by the preparation method of the present embodiment is the same as that of Fig. 2 (a) )same.
实施例8Example 8
水溶液法制备A2B(H2C3N3O3)4·4H2O(A＝K；B＝Mg)双折射晶体的方法，包括如下步骤：The method for preparing A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O (A=K; B=Mg) birefringent crystal by an aqueous solution method comprises the following steps:
1)将0.4mmol碳酸钾，0.2mmol氢氧化镁，1.2mmol氰尿酸溶解于80mL水中；1) 0.4mmol potassium carbonate, 0.2mmol magnesium hydroxide, 1.2mmol cyanuric acid are dissolved in 80mL water;
2)将装有步骤1)混合水溶液的烧杯放在磁力搅拌器上加热至80摄氏度并在加热过程中不断搅拌，直到溶液被加热浓缩到60mL，而后冷却结晶，三天后大量无色的透明单晶出现。2) The beaker containing the mixed aqueous solution in step 1) was heated to 80 degrees Celsius on a magnetic stirrer and stirred continuously during the heating process until the solution was heated and concentrated to 60 mL, and then cooled and crystallized. After three days, a large number of colorless transparent single crystal appears.
3)将步骤2)得到的晶体用冷水洗涤后随后放入干燥器中自然挥发水分，将得到双折射晶体进行XRD的测试，本实施例制备方法所得产品的X射线衍射图谱与图2(b)相同。3) the crystal obtained in step 2) is washed with cold water and then put into the dryer to naturally volatilize moisture, the birefringent crystal will be obtained and carry out the test of XRD. )same.
实施例9Example 9
水溶液法制备A2B(H2C3N3O3)4·4H2O(A＝Rb；B＝Ca)双折射晶体的方法，包括如下步骤：The method for preparing A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O (A=Rb; B=Ca) birefringent crystal by an aqueous solution method comprises the following steps:
1)将0.4mmol碳酸铷，0.2mmol氢氧化钙，1.2mmol氰尿酸溶解于70mL水中；1) 0.4mmol rubidium carbonate, 0.2mmol calcium hydroxide, 1.2mmol cyanuric acid are dissolved in 70mL water;
2)将装有步骤1)混合水溶液的烧杯放在磁力搅拌器上加热至80摄氏度搅拌，直到溶液被加热浓缩到60mL，而后冷却结晶，三天后大量无色的透明单晶出现。2) Put the beaker containing the mixed aqueous solution in step 1) on a magnetic stirrer and heat it to 80 degrees Celsius and stir until the solution is heated and concentrated to 60 mL, and then cooled to crystallize. After three days, a large number of colorless and transparent single crystals appeared.
3)将步骤2)得到的晶体用冷水洗涤后随后放入干燥器中自然挥发水分，将得到双折射晶体进行XRD的测试，本实施例制备方法所得产品的X射线衍射图谱与图2(c)相同。3) the crystal obtained in step 2) is washed with cold water and then put into the desiccator to naturally volatilize water, the birefringent crystal will be obtained and carry out the test of XRD, the X-ray diffraction pattern of the product obtained by the preparation method of the present embodiment is the same as that of Fig. 2 (c )same.
实施例10Example 10
水溶液法制备A2B(H2C3N3O3)4·4H2O(A＝K；B＝Ca)双折射晶体的方法，包括如下步骤：The method for preparing A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O (A=K; B=Ca) birefringent crystal by an aqueous solution method comprises the following steps:
1)将0.4mmol氢氧化钾，0.2mmol氢氧化钙，0.8mmol氰尿酸溶解于70mL水中；1) 0.4mmol potassium hydroxide, 0.2mmol calcium hydroxide, 0.8mmol cyanuric acid are dissolved in 70mL water;
2)将装有步骤1)混合水溶液的烧杯放在磁力搅拌器上加热至80摄氏度并在加热过程中不断搅拌，直到溶液被加热浓缩到60mL，而后冷却结晶，三天后大量无色的透明单晶出现。2) The beaker containing the mixed aqueous solution in step 1) was heated to 80 degrees Celsius on a magnetic stirrer and stirred continuously during the heating process until the solution was heated and concentrated to 60 mL, and then cooled and crystallized. After three days, a large number of colorless transparent single crystal appears.
3)将步骤2)得到的晶体用冷水洗涤后随后放入干燥器中自然挥发水分，将得到双折射晶体进行XRD的测试，本实施例制备方法所得产品的X射线衍射图谱与图2(a)相同。3) the crystal obtained in step 2) is washed with cold water and then put into the desiccator to naturally volatilize water, the birefringent crystal will be obtained and carry out the test of XRD, the X-ray diffraction pattern of the product obtained by the preparation method of the present embodiment is the same as that of Fig. 2 (a) )same.
实施例11Example 11
水溶液法制备A2B(H2C3N3O3)4·4H2O(A＝K；B＝Mg)双折射晶体的方法，包括如下步骤：The method for preparing A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O (A=K; B=Mg) birefringent crystal by an aqueous solution method comprises the following steps:
1)将0.4mmol氢氧化钾，0.2mmol氢氧化镁，0.8mmol氰尿酸溶解于60mL水中；1) 0.4mmol potassium hydroxide, 0.2mmol magnesium hydroxide, 0.8mmol cyanuric acid are dissolved in 60mL water;
2)将装有步骤1)混合水溶液的烧杯放在磁力搅拌器上加热至80摄氏度并不断加热搅拌，直到溶液被加热浓缩到50mL，而后冷却结晶，三天后大量无色的透明单晶出现。2) The beaker containing the mixed aqueous solution in step 1) was heated to 80 degrees Celsius on a magnetic stirrer and heated and stirred continuously until the solution was heated and concentrated to 50 mL, and then cooled and crystallized. After three days, a large number of colorless and transparent single crystals appeared.
3)将步骤2)得到的晶体用冷水洗涤后随后放入干燥器中自然挥发水分，将得到双折射晶体进行XRD的测试，本实施例制备方法所得产品的X射线衍射图谱与图2(b)相同。3) the crystal obtained in step 2) is washed with cold water and then put into the dryer to naturally volatilize moisture, the birefringent crystal will be obtained and carry out the test of XRD. )same.
实施例12Example 12
水溶液法制备A2B(H2C3N3O3)4·4H2O(A＝Rb；B＝Ca)双折射晶体的方法，包括如下步骤：The method for preparing A 2 B(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O (A=Rb; B=Ca) birefringent crystal by an aqueous solution method comprises the following steps:
1)将0.4mmol碳酸铷，0.2mmol氢氧化钙，0.8mmol氰尿酸溶解于60mL水中；1) 0.4mmol rubidium carbonate, 0.2mmol calcium hydroxide, 0.8mmol cyanuric acid are dissolved in 60mL water;
2)将装有步骤1)混合水溶液的烧杯放在磁力搅拌器上加热至80摄氏度并在加热过程中不断搅拌，直到溶液被加热浓缩到40mL，而后冷却结晶，三天后大量无色的透明单晶出现。2) The beaker containing the mixed aqueous solution in step 1) was heated to 80 degrees Celsius on a magnetic stirrer and stirred continuously during the heating process until the solution was heated and concentrated to 40 mL, and then cooled and crystallized. After three days, a large number of colorless transparent single crystal appears.
3)将步骤2)得到的晶体用冷水洗涤后随后放入干燥器中自然挥发水分，将得到双折射晶体进行XRD的测试，本实施例制备方法所得产品的X射线衍射图谱与图2(c)相同。3) the crystal obtained in step 2) is washed with cold water and then put into the desiccator to naturally volatilize water, the birefringent crystal will be obtained and carry out the test of XRD, the X-ray diffraction pattern of the product obtained by the preparation method of the present embodiment is the same as that of Fig. 2 (c )same.
实施例13渥拉斯顿棱镜Example 13 Wollaston Prism
如图3所示，加工两块光轴互相垂直的采用实施例1的K2Ca(H2C3N3O3)4·4H2O晶体材料制作的棱镜并将它们粘合起来，制成偏振分束棱镜，当一光束垂直入射到该棱镜端面后，在棱镜1中，o光和e光以不同速度沿相同方向行进；光从棱镜1进入棱镜2时，光轴旋转了90度，此时o光变为e光，偏离法线传播；e光变为o光，靠近法线传播。两束光线进入空气后，均是由光密介质传播到光疏介质，因此可以得到进一步分开的两束线偏振光。As shown in Figure 3, two prisms made of the K 2 Ca(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O crystal material of Example 1 were processed and bonded together to make A polarized beam splitting prism, when a light beam is vertically incident on the end face of the prism, in prism 1, the o light and the e light travel in the same direction at different speeds; when the light enters prism 2 from prism 1, the optical axis rotates 90 degrees , at this time, the o light becomes the e light, which propagates away from the normal; the e light becomes the o light, which propagates close to the normal. After the two beams of light enter the air, they both propagate from the optically denser medium to the optically sparser medium, so two further separated linearly polarized beams can be obtained.
实施例14偏振棱镜Example 14 Polarizing Prism
将两块实施例2得到的K2Mg(H2C3N3O3)4·4H2O晶体加工后，用加拿大树胶粘结(或空气隙)，制作成如图4所示的偏振棱镜。当一束光垂直于棱镜端面入射后，在第一块棱镜中o光和e光均不发生偏折；在胶合面o光发生全反射，并被棱镜直角面上的吸收涂层所吸收，而e光无偏折地从第二块棱镜出射。Two pieces of K 2 Mg(H 2 C 3 N 3 O 3 ) 4 · 4H 2 O crystals obtained in Example 2 were processed and bonded with Canadian gum (or air gap) to make the polarization as shown in Figure 4 Prism. When a beam of light is incident perpendicular to the end face of the prism, neither the o light nor the e light will be deflected in the first prism; the o light will be totally reflected on the glued surface and absorbed by the absorbing coating on the right-angle surface of the prism, The e-light emerges from the second prism without deflection.
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The embodiments of the present invention have been described above. However, the present invention is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
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| CN115976646A (en) * | 2022-09-06 | 2023-04-18 | 中国科学院福建物质结构研究所 | A kind of crystal material and its preparation method and application |
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| CN114635190A (en) * | 2022-03-22 | 2022-06-17 | 季华实验室 | A kind of organic-inorganic hybrid birefringent crystal and its preparation method and application |
| CN114635190B (en) * | 2022-03-22 | 2023-03-24 | 季华实验室 | Organic-inorganic hybrid birefringent crystal and preparation method and application thereof |
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| CN115652405A (en) * | 2022-11-10 | 2023-01-31 | 中国科学院福建物质结构研究所 | NH 4 (H 2 C 6 N 7 O 3 )·2H 2 O compound, birefringent crystal, and production method and use thereof |
| CN115924956A (en) * | 2022-12-14 | 2023-04-07 | 中国科学院新疆理化技术研究所 | Compound rubidium hydroxyfluoborate, rubidium hydroxyfluoborate nonlinear optical crystal, preparation method and application |
| CN115924956B (en) * | 2022-12-14 | 2024-04-30 | 中国科学院新疆理化技术研究所 | Compound rubidium hydroxyfluoride borate, rubidium hydroxyfluoride borate nonlinear optical crystal, preparation method and application |
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