CN109137071A - Barium magnesium cyanurate birefringent crystal for ultraviolet visible wave band and preparation method and application thereof - Google Patents

Barium magnesium cyanurate birefringent crystal for ultraviolet visible wave band and preparation method and application thereof Download PDF

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Publication number
CN109137071A
CN109137071A CN201810659730.0A CN201810659730A CN109137071A CN 109137071 A CN109137071 A CN 109137071A CN 201810659730 A CN201810659730 A CN 201810659730A CN 109137071 A CN109137071 A CN 109137071A
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crystal
birefringece crystal
wave band
prism
barium magnesium
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姚吉勇
李壮
郭扬武
罗晓宇
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Technical Institute of Physics and Chemistry of CAS
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Technical Institute of Physics and Chemistry of CAS
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    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10Inorganic compounds or compositions
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B11/00Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method

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  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a barium magnesium cyanurate birefringent crystal used for ultraviolet visible wave band, a preparation method and application thereof, wherein the chemical formula is Ba2Mg(C3N3O3)2Belonging to the trigonal system, the space group isCell parameters ofZ is 3; the crystal is grown by adopting a high-temperature melt spontaneous crystallization method or a crucible descent method, the barium magnesium cyanurate birefringent crystal obtained by the method is a negative uniaxial crystal, the transmission range is 230-3000nm, and the calculated value of the refractive index at the position of lambda-800 nm is no=2.00,ne1.649, Δ n is 0.351. The crystal is easy to grow, cut, grind, polish and store, is stable in air, is not easy to deliquesce and is insoluble in water; the method can be used for manufacturing polarization beam splitting prisms such as a Glan prism, a Wollaston prism, a Rochon prism or a beam splitting polarizer; has important application in the fields of optics and communication.

Description

It is a kind of for the Cyanuric Barium magnesium birefringece crystal of UV, visible light wave band and its preparation side Method and application
Technical field
The present invention relates to a kind of cyanurate birefringece crystal, the chemical formula for being particularly suitable for UV, visible light wave band is Ba2Mg(C3N3O3)2Birefringece crystal and its preparation method and application.
Background technique
Birefringent phenomenon is one of the important feature showed when light is propagated in anisotropic medium.When light is incident on It when in anisotropic medium, is decomposed into two-beam and reflects in different directions, the two-beam of outgoing is direction of vibration phase Mutually vertical linearly polarized light, wherein it is a branch of defer to the law of refraction be known as ordinary light (o light), refractive index noIt indicates, it is another Beam does not defer to the referred to as non-ordinary light (e light) of the law of refraction, refractive index neIt indicating, this phenomenon is known as birefringent phenomenon, In have anisotropic crystal be known as birefringece crystal.Using this property of birefringece crystal, available linearly polarized light, The displacement etc. to light beam is realized, so that birefringece crystal becomes the photoelectricity such as manufacture polarization polarizing prism, polarization beam splitter prism The important materials of original part have important application in optics and communication field.
Common birefringent material mainly has calcite (CaCO3), rutile (TiO2)、YVO4、LiNbO3、MgF2Crystal and Quartz crystal etc..Calcite crystal is mainly to be naturally occurring, and artificial synthesized difficulty, general crystalline size is smaller, Bu Nengman The demand of sufficient large-size crystals element, in addition it is also unable to reach ultraviolet region using wave band;There is also similar for rutile crystal The problem of, artificial synthesized difficulty cannot be used in ultraviolet band, and such hardness of crystals is big, and processing device difficulty is big;YVO4 And LiNbO3Crystal can grow large size single crystal, but LiNbO3Crystal birefringence rate is smaller, and both crystal can not For ultraviolet band;MgF2Crystal and quartz crystal can be used for the crystal of ultraviolet band, but their birefringence is too It is small, limit the use of crystal.The birefringece crystal that can be used for ultraviolet band reported in recent years has α-bbo crystal and Ca3 (BO3)2Crystal.High-temperature-phase BaB2O4The transmission range of (α-BBO) crystal is 189-3500nm, and birefringence is larger, but crystal It easily deliquesces, and since crystal is there are solid-state phase changes, is easy to crack during the growth process, has larger impact to crystal quality;
Ca3(BO3)2The transmission range of crystal is 180-3800nm, the disadvantage is that it is birefringent less than normal in visual field, in ultraviolet waves Section area transmission is not high, limits its use.
Summary of the invention
It is an object of the present invention to provide a kind of cyanurate birefringece crystal for UV, visible light wave band, the crystalline substances Body is easy to grow, is easy to cut, being easy to grind, be easily polished and be easy to save, stable in the air, is not easy to deliquesce, not dissolve in Water.
Another object of the present invention is to provide the growth side of the cyanurate birefringece crystal for UV, visible light wave band Method.
Still a further object of the present invention is to provide the cyanuric acid birefringece crystal for UV, visible light wave band and polarizes in production Application in beam splitter prism.
To achieve the goals above, technical scheme is as follows:
Provided by the present invention for the cyanurate birefringece crystal of UV, visible light wave band, chemical formula Ba2Mg (C3N3O3)2, as shown in Figure 1, the crystal belongs to trigonal system, space group isCell parameter isZ=3.Ba2Mg(C3N3O3)2Crystal penetrates model It encloses for 230-3000nm;The refractive index calculated value at λ=800nm are as follows: no=2.00, ne=1.649, Δ n=0.351;Crystal is easy In growth, it is easy to cut, be easy to grind, be easily polished and be easy to save, it is stable in the air, be not easy to deliquesce, it is not soluble in water.
The growing method of cyanurate birefringece crystal for UV, visible light wave band of the invention, uses high-temperature fusant Spontaneous crystallization method or Bridgman-Stockbarge method for growing crystal.
The high-temperature fusant spontaneous crystallization method growth crystal includes the following steps:
By containing barium compound, magnesium-containing compound and radical compound containing cyanic acid by wherein barium: magnesium: molar ratio=2 of cyanate radical: After mixing, compound is heated to melting obtaining high temperature solution and after being kept for 24-96 hours to the ratio of 1:6, with 1-10 DEG C/h Rate be cooled to room temperature, obtain colorless and transparent Ba2Mg(C3N3O3)2Crystal.
Preferably, the containing barium compound is BaCl2Or BaBr2Or BaI2
Preferably, the magnesium-containing compound is MgCl2Or MgBr2Or MgI2
Preferably, the radical compound containing cyanic acid is LiCNO or NaCNO or KCNO.
Ba provided by the invention2Mg(C3N3O3)2Another preparation method of birefringece crystal, is Bridgman-Stockbarge method for growing Ba2Mg(C3N3O3)2Birefringece crystal comprising following steps:
By powdered Ba2Mg(C3N3O3)2Compound is put into crystal growing apparatus, is to slowly warm up to melting sources, to original After material is completely melt, crystal growing apparatus is vertically declined with the speed of 0.1-10mm/h, during crystal growing apparatus decline Carry out Ba2Mg(C3N3O3)2Birefringece crystal growth, growth cycle are 5-20 days;
The powdered Ba2Mg(C3N3O3)2Preparing for compound is as follows:
Containing barium compound, magnesium-containing compound and radical compound containing cyanic acid are by wherein barium: magnesium: molar ratio=2:1 of cyanate radical: After mixing, be heated to 400 DEG C of progress solid phase reactions (in principle, can be made using general chemical synthesis process 6 ratio Standby Ba2Mg(C3N3O3)2Compound;The preferred solid reaction process of the present invention), then by-product is removed with methanol repeated flushing Formula is Ba2Mg(C3N3O3)2Compound, smashed to pieces and grind to obtain powdered Ba2Mg(C3N3O3)2Compound;
The containing barium compound is BaCl2Or BaBr2Or BaI2
The magnesium-containing compound is MgCl2Or MgBr2Or MgI2
The radical compound containing cyanic acid is LiCNO or NaCNO or KCNO.
The Ba2Mg(C3N3O3)2Compound can be prepared by following chemical equations:
(1)2BaCl2+MgCl2+ 6KCNO=Ba2Mg(C3N3O3)2+6KCl;
(2)2BaBr2+MgBr2+ 6KCNO=Ba2Mg(C3N3O3)2+6KBr;
(3)2BaI2+MgI2+ 6KCNO=Ba2Mg(C3N3O3)2+6KI;
(4)2BaCl2+MgCl2+ 6NaCNO=Ba2Mg(C3N3O3)2+6NaCl;
(5)2BaBr2+MgBr2+ 6NaCNO=Ba2Mg(C3N3O3)2+6NaBr;
(6)2BaI2+MgI2+ 6NaCNO=Ba2Mg(C3N3O3)2+6NaI;
(7)2BaCl2+MgCl2+ 6LiCNO=Ba2Mg(C3N3O3)2+6LiCl;
(8)2BaBr2+MgBr2+ 6LiCNO=Ba2Mg(C3N3O3)2+6LiBr;
(9)2BaI2+MgI2+ 6LiCNO=Ba2Mg(C3N3O3)2+6LiI。
Ba having a size of Centimeter Level can get using above two method2Mg(C3N3O3)2Birefringece crystal;Use big ruler Very little crucible, and extend growth period, then it can get corresponding larger size Ba2Mg(C3N3O3)2Birefringece crystal.
Ba provided by the invention2Mg(C3N3O3)2The transmission range of birefringece crystal is wide (230-3000nm), and calculates double Big (the n at λ=800nm of refractive index valueo-ne=0.351) it, can be used for UV, visible light wave band, and crystal is easy to grow, it is easy to process, It is not easy to deliquesce.
Provided by the present invention for the purposes of the cyanurate birefringece crystal of UV, visible light wave band, the cyanurate is double Refracting crystal is Ba2Mg(C3N3O3)2Birefringece crystal, for making polarization beam splitter prism.The polarization beam splitter prism is lattice Flange-type prism, wollaston prism, Rochon prism or light beam separate polarizer.
Cyanurate birefringece crystal for UV, visible light wave band of the invention has the advantage that as follows:
Cyanurate birefringece crystal for UV, visible light wave band of the invention is Ba2Mg(C3N3O3)2Birefringece crystal, It is wide (230-3000nm) through range, birefringent big (Δ n=0.351 at 800nm), can be used for UV, visible light wave band;Crystal It is easy to cut, be easy to grind, be easily polished and be easy to save, it is stable in the air, be not easy to deliquesce, production polarization beam splitter prism Aspect can be used widely.
Detailed description of the invention
Fig. 1 is the Ba for UV, visible light wave band2Mg(C3N3O3)2The structure chart of birefringece crystal;
Fig. 2 is with the Ba for UV, visible light wave band of the invention2Mg(C3N3O3)2Birefringece crystal makes Glan type prism Schematic diagram;
Fig. 3 is with the Ba for UV, visible light wave band of the invention2Mg(C3N3O3)2Birefringece crystal makes Wollaston rib The schematic diagram of mirror;
Fig. 4 is with the Ba for UV, visible light wave band of the invention2Mg(C3N3O3)2Birefringece crystal makes Rochon prism Schematic diagram;
Fig. 5 is with the Ba for UV, visible light wave band of the invention2Mg(C3N3O3)2It is inclined that birefringece crystal makes light beam separation The schematic diagram of vibration device.
Specific embodiment
Any feature is disclosed to obtain in this specification, it unless specifically stated, can be equivalent or with similar purpose by other Alternative features are replaced.Unless specifically stated, each feature is an example in a series of equivalent or similar characteristics ?.It is described to understand the present invention just for the sake of help, it should not be considered as to concrete restriction of the invention.
With the drawings and specific embodiments, the present invention is described in further detail below.
Embodiment 1 prepares Ba using high-temperature fusant spontaneous crystallization method2Mg(C3N3O3)2Crystal:
Weigh 4.166 grams of BaCl2, 0.952 gram of MgCl2With 4.866 grams of KCNO (i.e. BaCl2: MgCl2: KCNO= 0.02mol:0.01mol:0.06mol), after evenly mixing, it is fitted into the quartz glass tube of Φ 20mm × 100mm, is evacuated to 10-3It after pa, is packaged and placed in tubular type growth furnace with oxyhydrogen flame, is slowly increased to 500 DEG C, constant temperature 72 hours, with the rate of 1 DEG C/h Slow cooling closes tubular type growth furnace to room temperature;It is cut after quartz ampoule is cooling, colorless and transparent Ba can be obtained2Mg(C3N3O3)2 Crystal.
Embodiment 2 prepares Ba using Bridgman-Stockbarger method2Mg(C3N3O3)2Crystal:
Weigh 8.332 grams of BaCl2, 1.904 grams of MgCl2With 9.732 grams of KCNO (BaCl2: MgCl2: KCNO=0.04mol: 0.02mol:0.12mol), after evenly mixing, it is fitted into the quartz glass tube of Φ 25mm × 200mm, is evacuated to 10-3After pa, It is packaged and placed in tubular type growth furnace with oxyhydrogen flame, being slowly increased to 400 DEG C makes raw material solid phase react 96h, tubular type growth furnace is closed, It will obtain product methanol repeated flushing and remove by-product KCl, and grind to obtain Ba after dry2Mg(C3N3O3)2Powder.By Ba2Mg (C3N3O3)2Powder is fitted into the quartz glass tube of Φ 25mm × 200mm, is evacuated to 10-3After pa, postposition is encapsulated with oxyhydrogen flame In crystal growing furnace, 500 DEG C are slowly increased to after raw material is completely melt, grower was hung down with 0.1-10mm/ hours speed Straight decline;After crystal growth, grower was down to room temperature with 50 hours, obtained colorless and transparent Ba2Mg(C3N3O3)2It is brilliant Body.
After tested, Ba prepared by above-described embodiment 1-22Mg(C3N3O3)2Birefringece crystal category just belongs to trigonal system, empty Between group beCell parameter isZ=3;Through model It encloses for 230-3000nm;The refractive index calculated value at λ=800nm are as follows: no=2.00, ne=1.649, Δ n=0.351;Fig. 1 is The Ba2Mg(C3N3O3)2The structural schematic diagram of birefringece crystal.
Embodiment 3, with the Ba for UV, visible light wave band of the invention2Mg(C3N3O3)2Birefringece crystal makes Glan type Prism:
Utilize Ba2Mg(C3N3O3)2Crystal-Canada's resin (or thin layer of air)-Ba2Mg(C3N3O3)2Crystal constitutes Glan Type prism (Fig. 2), crystal ne<no.When incident light is perpendicular to prism surface feeding sputtering, deviation does not occur for o light and e light, on inclined-plane On incidence angle be equal to prism hypotenuse/facet surfaces and right-angle surface angle.Make prism hypotenuse/facet surfaces and the angle of right-angle surface be greater than o light when production to exist Critical angle on cemented surface, such o light will be totally reflected on cemented surface, and are absorbed or led to by the coating in prism right-angle surface It crosses outside o light to rush down and be rushed down outside window, and e light without deviation is emitted from prism since refractive index is almost unchanged.
Embodiment 4, with Ba of the invention2Mg(C3N3O3)2Birefringece crystal makes wollaston prism:
By two Ba2Mg(C3N3O3)2Crystal prism bonding constitutes wollaston prism (Fig. 3), the birefringent crystalline substance of two of them The optical axis of body prism is mutually perpendicular to.Incident light impinges perpendicularly on prism end face, and in prism 1, o light and e light are with friction speed edge Same direction is advanced, and when light enters prism 2 from prism 1, optical axis has turned 90 degree, and o light becomes e light, and e light becomes o light, into after air, It is that optically thinner medium is entered by optically denser medium, two bunch polarised lights being spaced further apart.Birefringence is bigger, is more conducive to The separation of light beam.
Embodiment 5, with Ba of the invention2Mg(C3N3O3)2Birefringece crystal makes Rochon prism:
By two Ba2Mg(C3N3O3)2Crystal prism bonding constitutes Rochon prism (Fig. 4), two of them birefringece crystal rib The optical axis of mirror is mutually perpendicular to.Incident light impinges perpendicularly on prism end face, and light is propagated along optical axis direction in the first prism, do not produced Life is birefringent, and o light, e light are all advanced with o ray velocity in the same direction.Into after the second prism, optical axis turns over 90 degree, is parallel to The e light of drawing vibration becomes o light in the second prism, this Shu Guang speed in two pieces of prisms is constant, the injection prism of no deviation. Become e light in the second prism perpendicular to the o light of drawing vibration, obtains the mutually perpendicular linear polarization of the separated direction of vibration of two beams Light.
Embodiment 6, with Ba of the invention2Mg(C3N3O3)2Birefringece crystal makes light beam and separates polarizer:
Process a Ba2Mg(C3N3O3)2Birefringece crystal makes its axial plane and rib at 45 degree of angles (Fig. 5).When incident light hangs down After straight incidence, two-beam separation, birefringence is bigger, is more conducive to the separation of light beam.
Technological parameter (such as temperature, time) section bound value of the invention and interval value can realize this law, Embodiment numerous to list herein.
Ordinary skill in the art knowledge can be used in the unspecified content of the present invention.
It should be noted last that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting.Although ginseng It is described the invention in detail according to embodiment, it will be apparent to an ordinarily skilled person in the art that technical side of the invention Case is modified or replaced equivalently, and without departure from the spirit and scope of technical solution of the present invention, should all be covered in the present invention Scope of the claims in.

Claims (7)

1. a kind of Cyanuric Barium magnesium birefringece crystal for UV, visible light wave band, which is characterized in that the Cyanuric Barium magnesium is double The chemical formula of refracting crystal is Ba2Mg(C3N3O3)2, belong to trigonal system, space group isCell parameter isZ=3;Through range 230-3000nm, λ= Refractive index calculated value n at 800nmo=2.00, ne=1.649, Δ n=0.351.
2. the preparation method described in a kind of claim 1 for the Cyanuric Barium magnesium birefringece crystal of UV, visible light wave band, described Preparation method is to grow Ba using high-temperature fusant spontaneous crystallization method2Mg(C3N3O3)2Birefringece crystal is raw using Bridgman-Stockbarger method Long Cyanuric Barium magnesium birefringece crystal.
3. the preparation method for the Cyanuric Barium magnesium birefringece crystal of UV, visible light wave band according to claim 2, special Sign is that the high-temperature fusant spontaneous crystallization method grows Ba2Mg(C3N3O3)2Birefringece crystal comprising following steps:
By containing barium compound, magnesium-containing compound and radical compound containing cyanic acid by wherein barium: magnesium: molar ratio=2:1:6 of cyanate radical Ratio be uniformly mixed and be heated to melting obtaining high temperature solution and after being kept for 24-96 hour, with 1-10 DEG C/h of rate of temperature fall drop It warms to room temperature, obtains Ba2Mg(C3N3O3)2Birefringece crystal.
4. the preparation method for the Cyanuric Barium magnesium birefringece crystal of UV, visible light wave band according to claim 3, special Sign is that the containing barium compound is BaCl2Or BaBr2Or BaI2
The magnesium-containing compound is MgCl2Or MgBr2Or MgI2
The radical compound containing cyanic acid is LiCNO or NaCNO or KCNO.
5. the preparation method for the Cyanuric Barium magnesium birefringece crystal of UV, visible light wave band according to claim 2, special Sign is, the Bridgman-Stockbarge method for growing Cyanuric Barium magnesium birefringece crystal comprising following steps:
By Ba2Mg(C3N3O3)2Polycrystalline powder is put into crystal growing apparatus, is to slowly warm up to melting sources, completely molten to raw material After change, crystal growing apparatus is vertically declined with the speed of 0.1-10mm/h, carries out cyanogen urine during crystal growing apparatus decline Sour barium magnesium birefringece crystal growth, growth cycle are 5-20 days.
6. the Cyanuric Barium magnesium birefringece crystal described in claim 1 for UV, visible light wave band is in production polarization beam splitter prism In application.
7. the Cyanuric Barium magnesium birefringece crystal according to claim 6 for UV, visible light wave band is in production polarization beam splitting Application in prism, which is characterized in that the polarization beam splitter prism is Glan type prism, wollaston prism, Rochon prism Or light beam separates polarizer.
CN201810659730.0A 2018-06-25 2018-06-25 Barium magnesium cyanurate birefringent crystal for ultraviolet visible wave band and preparation method and application thereof Pending CN109137071A (en)

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CN111499588A (en) * 2019-01-31 2020-08-07 中国科学院理化技术研究所 Ba2M(C3N3O3)2Compound, crystal thereof, preparation method and application of crystal
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CN111945228B (en) * 2019-05-14 2021-05-28 中国科学院理化技术研究所 Birefringent crystal material, preparation method and application thereof
CN110184642A (en) * 2019-07-08 2019-08-30 中国工程物理研究院化工材料研究所 A kind of UV, visible light wave band birefringece crystal and powder and preparation method thereof
CN110499531A (en) * 2019-09-29 2019-11-26 中国工程物理研究院化工材料研究所 A kind of novel bromine barium cyanate birefringece crystal and preparation method thereof
CN110499531B (en) * 2019-09-29 2020-07-07 中国工程物理研究院化工材料研究所 Barium bromocyanurate birefringent crystal and preparation method thereof
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

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