CN111945228A - Birefringent crystal material, preparation method and application thereof - Google Patents

Birefringent crystal material, preparation method and application thereof Download PDF

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CN111945228A
CN111945228A CN201910400046.5A CN201910400046A CN111945228A CN 111945228 A CN111945228 A CN 111945228A CN 201910400046 A CN201910400046 A CN 201910400046A CN 111945228 A CN111945228 A CN 111945228A
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crystal
magnesium
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CN111945228B (en
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李如康
孟祥鹤
夏明军
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Technical Institute of Physics and Chemistry of CAS
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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

Birefringent crystal material, preparation method and application thereof
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:
Figure BDA0002059477560000021
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). Superior foodOptionally, the K is2Mg(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:
Figure BDA0002059477560000022
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:
Figure BDA0002059477560000031
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
Aqueous solution processPreparation of A2B(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; e light becomes o light byNear normal propagation. 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; the light o is totally reflected on the bonding surface and absorbed by the absorbing coating on the right-angle surface of the prism, and the light e exits 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 (10)

1. A crystalline material of 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.
2. The crystalline material of claim 1, wherein the crystalline material is K2Mg(H2C3N3O3)4·4H2O, the unit cell parameters of which are:
Figure FDA0002059477550000011
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).
3. The crystalline material of claim 1, wherein the crystalline material is K2Ca(H2C3N3O3)4·4H2O, the unit cell parameters of which are:
Figure FDA0002059477550000012
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).
4. The crystalline material of claim 1, wherein the crystalline material is Rb2Ca(H2C3N3O3)4·4H2O, the unit cell parameters are:
Figure FDA0002059477550000013
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).
5. According to claim1-4, wherein each two adjacent [ H ] s in the crystal structure thereof2C3N3O3]-The groups are connected through hydrogen bonds (H-N … H), and A ions and B ions are filled in [ H ]2C3N3O3]-Among the ribbon-like structures composed of radicals;
preferably, the birefringence of the crystal material is 0.3-0.4 at 800 nm;
preferably, the transmittance of the crystal material in the spectral range of 200-;
preferably, the ultraviolet absorption cut-off wavelength of the crystal material is 230-240 nm;
preferably, the crystalline material is a colorless transparent crystal.
6. A method for the preparation of a crystalline material as claimed in any one of claims 1 to 5, characterized in that the method comprises 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.
7. The preparation method according to claim 6, wherein the molar volume ratio of the potassium element and/or rubidium element, the calcium element and/or magnesium element, the cyanuric acid to the water is (0.1-20) mmol, (0.3-50) mmol, (0.2-90) mL;
preferably, the heating temperature is 40-100 ℃;
preferably, the degree of heating is: until the volume of the mixed solution is reduced to 45-95% of the initial volume of the mixed solution;
preferably, the potassium element-containing compound is selected from at least one of potassium nitrate, potassium chloride, potassium oxide, potassium fluoride, potassium iodide, potassium carbonate, potassium hydroxide, and potassium fluoroborate;
preferably, the rubidium element-containing compound is at least one selected from rubidium nitrate, rubidium chloride, rubidium oxide, rubidium fluoride, rubidium iodide, rubidium carbonate, rubidium hydroxide and rubidium fluoroborate;
preferably, the calcium element-containing compound is selected from at least one of calcium nitrate, calcium chloride, calcium oxide, calcium fluoride, calcium iodide, calcium carbonate, calcium hydroxide, and calcium fluoroborate;
preferably, the elemental magnesium-containing compound is selected from at least one of magnesium nitrate, magnesium chloride, magnesium oxide, magnesium fluoride, magnesium iodide, magnesium carbonate, magnesium hydroxide, and magnesium fluoroborate.
8. Use of the crystalline material of any one of claims 1 to 5 as a birefringent crystalline material.
9. Use of the crystalline material of any one of claims 1-5 in an optical device;
preferably, the optical device is an optical polarizer, a beam displacer, a circulator, an optical isolator or an optical modulator.
10. An optical polarizer comprising the crystalline material of any one of claims 1 to 5;
preferably, the optical polarizer is a polarizing beam splitting prism;
preferably, the polarization beam splitter prism is a glantrier prism, a wollaston prism or a rochon prism.
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