CN115874289A - Large-size guanidino tetrafluoroborate birefringent crystal, and growth method and application thereof - Google Patents
Large-size guanidino tetrafluoroborate birefringent crystal, and growth method and application thereof Download PDFInfo
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- CN115874289A CN115874289A CN202211670253.0A CN202211670253A CN115874289A CN 115874289 A CN115874289 A CN 115874289A CN 202211670253 A CN202211670253 A CN 202211670253A CN 115874289 A CN115874289 A CN 115874289A
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- 239000013078 crystal Substances 0.000 title claims abstract description 259
- -1 guanidino tetrafluoroborate Chemical compound 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 44
- 230000003287 optical effect Effects 0.000 claims abstract description 35
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- 230000005540 biological transmission Effects 0.000 claims abstract description 5
- 239000012047 saturated solution Substances 0.000 claims description 70
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 10
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
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- 238000002156 mixing Methods 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 1
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- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
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- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
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- QWVYNEUUYROOSZ-UHFFFAOYSA-N trioxido(oxo)vanadium;yttrium(3+) Chemical compound [Y+3].[O-][V]([O-])([O-])=O QWVYNEUUYROOSZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a large-size guanidyl tetrafluoroborate birefringent crystal with a molecular formula of CN, a growth method and application thereof 3 H 6 BF 4 Molecular weight of 146.90, belonging to trigonal system, and space group ofR3mCell parameter ofa=7.4445(4)Å，b=7.4445(4)Å，c=9.1025(9)Å，α=90.00°，β=90.00°，γ=120.00°，Z=3，V=436.88 (5); the crystals are permeableThe over range is 190-2450nm, the birefringence is 0.12@546nm, and the crystal is grown by an aqueous solution cooling method. The crystal has large birefringence, wide transmission range, easy growth and processing, and can be used as birefringent crystal. The crystal is used for manufacturing a polarization beam splitter prism or an optical element of an infrared-visible-ultraviolet-deep ultraviolet waveband, and has important application in the aspects of manufacturing optical beam splitter prisms such as a Glan prism, a Rochon prism, a Nicole prism, a Wollaston prism, a Sannamont prism and the like, a beam splitter, an optical isolator, a circulator, a beam shifter, a polarizer, an analyzer, an optical polarizer, a phase delay device, an electro-optical modulator and the like.
Description
Technical Field
The invention relates to a molecular formula CN for infrared-visible-ultraviolet-deep ultraviolet band 3 H 6 BF 4 The growth method and the application of the large-size guanidyl tetrafluoroborate crystal belong to the technical field of crystal materials and the technical field of optics.
Background
When a light beam enters an anisotropic crystal material, a phenomenon in which the light beam is decomposed into two beams and refracted in different directions is called a birefringence phenomenon, and the two beams generated by birefringence are linearly polarized light having polarization directions perpendicular to each other. With the continuous expansion of the application range and depth of laser and the rapid development of optical communication technology, birefringent crystals have become indispensable important materials for modulating the polarization state of light. At present, birefringent crystals are key materials for manufacturing polarization beam splitting prisms such as a Glan prism and a Wollaston prism, and optical communication elements such as an optical isolator, a beam shifter and a circulator. Birefringent crystals that are commonly used require as much birefringence as possible in the operating band.
The birefringent optical crystal has important application value in many fields, such as scientific research, traffic, national defense, industry and the like, and with the rapid development of laser industry and business, the search for a new birefringent material with good performance is urgent. The commonly used birefringent materials mainly include yttrium vanadate, barium metaborate, lithium niobate, calcite and the like. However, these birefringent materials have disadvantages: YVO 4 Is an artificial birefringent crystal with good performanceBut because of YVO 4 The melting point is high, an iridium crucible is required to be used for pulling growth, and the growth atmosphere is a weak oxygen atmosphere, so that the valence change problem of iridium exists during growth, the quality of crystals is reduced, and high-quality crystals are not easy to obtain; alpha-BaB 2 O 4 Due to the existence of solid phase transition, (alpha-BBO) is easy to crack in the crystal growth process; liNbO 3 The crystal is easy to obtain a large-size crystal, but the birefringence is too small; calcite crystals mainly existing in a natural form are difficult to artificially synthesize, generally have small sizes and high impurity content, cannot meet the requirements of large-size optical polarizing elements, are easy to dissociate, are difficult to process and have low crystal utilization rate. In view of the above, it is very necessary to find a birefringent crystal which has a large birefringence, good and stable overall performance parameters, and is easy to grow a high-quality large-size bulk crystal.
Since the eighties of the last century, guanidino tetrafluoroborates (CN) have been available 3 H 6 BF 4 ) The report of (1). In 1987, a.kozak et al studied the crystal structure of guanidino tetrafluoroborate (a.kozak, et al,1987, j.phys.c; in 1989, s.hauss uhl studied the thermoelectric, dielectric, piezoelectric and elastic properties of guanidinium tetrafluoroborate crystals (s.hauss uhl, 1989, z.kristallogr, 187,153); in 2018, s.nandhini et al studied structural, optical, mechanical, electrical, and nonlinear optics (s.nandhini, et al,2018, optics and Laser technology,105, 249). The crystal growth methods adopted in the existing documents are all slow evaporation methods, and no aqueous solution cooling method growth method is reported, and no application or research report of the crystal growth method as a birefringent crystal is reported. The growth method of the guanidino tetrafluoroborate birefringent crystal is an aqueous solution cooling method, and the guanidino tetrafluoroborate birefringent crystal is used as a birefringent crystal for preparing a multiband polarization beam splitting prism or an optical element.
Disclosure of Invention
The invention aims to provide a large-size guanidino tetrafluoroborate birefringent crystal with a molecular formula of CN 3 H 6 BF 4 Molecular weight of 146.90, belonging to trigonalCrystal system, space group is R3m, cell parameter is
α =90.00 °, β =90.00 °, γ =120.00 °, Z =3, v =436.88 (5); has wide light-transmitting wave band, transmission range of 190-2450nm, and birefringence of 0.12@546nm.
Another object of the present invention is to provide an aqueous solution growth method of large-size guanidino tetrafluoroborate birefringent crystal.
Still another object of the present invention is to provide a use of a large-size guanidino tetrafluoroborate birefringent crystal as a birefringent crystal.
The invention relates to a large-size guanidino tetrafluoroborate birefringent crystal, which has a molecular formula as follows: CN 3 H 6 BF 4 Molecular weight of 146.90, belonging to trigonal system, space group of R3m, and unit cell parameter of
α =90.00 °, β =90.00 °, γ =120.00 °, Z =3, v =436.88 (5); the crystal is grown by an aqueous solution cooling method, the transmission range of the crystal is 190-2450nm, and the birefringence is 0.12@546nm.
The method for growing the large-size guanidino tetrafluoroborate birefringent crystal adopts an aqueous solution cooling method to grow the crystal, and the specific operation is carried out according to the following steps:
a. mixing commercially available guanidine carbonate and fluoroboric acid according to a molar ratio of 1:2 for reaction to generate a crude product of guanidino tetrafluoroborate, then recrystallizing and drying to obtain high-purity guanidino tetrafluoroborate, and selecting high-quality transparent guanidino tetrafluoroborate seed crystals with millimeter-level sizes from the guanidino tetrafluoroborate seed crystals;
b. dissolving the high-purity guanidino tetrafluoroborate obtained in the step a by using deionized water, and preparing a saturated solution at the temperature of 30-60 ℃;
c. transferring 100-1000ml of the saturated solution in the step b to a crystal growth device by an aqueous solution cooling method, and then keeping the saturated solution at the saturation temperature of 30-60 ℃ for 2-24 hours;
d. b, fixing the guanidino tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then putting the seed crystal and the seed crystal frame into the crystal growth device in the step c to enable the seed crystal and the seed crystal frame to be located above the liquid level of the saturated solution; simultaneously, raising the temperature of the solution by 1-5 ℃ on the basis of the saturation temperature of 30-60 ℃, and preheating the seed crystals for 2-24 hours; then, completely immersing the seed crystal into the saturated solution, simultaneously cooling to a saturation temperature point, cooling at the speed of 0.01-1 ℃/day after the seed crystal reaches a growth equilibrium point, and keeping the rotation speed of the seed crystal at 5-50 rpm to carry out crystal growth;
e. after 6-60 days, obtaining colorless and transparent centimeter-sized large-size guanidino tetrafluoroborate birefringent crystals in a saturated solution in a crystal growth device, and finally taking out the crystals from the saturated solution.
The guanidino tetrafluoroborate birefringent crystal is applied to the preparation of multiband polarization beam splitting prisms or optical elements.
The polarization beam splitting prism is a Glan prism, a Wollaston prism, a Rochon prism, a Nicole prism or a Sannamont prism.
The optical element is a polarized beam splitter, an optical isolator, a circulator, a beam shifter, an optical polarizer, an optical analyzer, an optical polarizer, an optical modulator, a polarization beam splitter, a phase delay device or an electro-optical modulation device.
The manufactured polarization beam splitter prism or optical element is used for infrared-visible-ultraviolet-deep ultraviolet multiple wave bands.
The crystal growth device used is a self-made water bath.
The guanidyl tetrafluoroborate birefringent crystal has the light transmission range of 190-2450nm and the birefringence of 0.12@546nm, has the characteristics of high quality, large crystal size, good optical uniformity and the like, can meet the requirements of device manufacturing, and is easy to be widely applied to infrared-visible-ultraviolet-deep ultraviolet bands.
By adopting the method for growing the guanidino tetrafluoroborate birefringent crystal, the centimeter-sized large-size guanidino tetrafluoroborate crystal is obtained by the method, the layered growth habit is avoided, the crystal is easy to grow and is transparent and free of wrapping in the growth process of the crystal, and the method has the advantages of high growth speed, low energy consumption, low cost, easiness in obtaining large-size crystals and the like.
The guanidino tetrafluoroborate birefringent crystal grown by the growing method of the invention orients the crystal blank according to the crystallographic data of the crystal, cuts the crystal according to the required angle, thickness and section size, polishes the light-passing surface of the crystal, and can be used as a polarization beam splitter prism or an optical element.
Drawings
FIG. 1 is a structural diagram of a guanidino tetrafluoroborate crystal of the present invention: wherein (a) an X-ray diffraction pattern (b) a spatial structure diagram;
FIG. 2 is a photograph of a guanidino tetrafluoroborate crystal of the present invention;
FIG. 3 is a photograph of a prism used for measuring refractive index of a guanidino tetrafluoroborate crystal of the present invention;
FIG. 4 is a schematic view of a Gram prism made from the crystal obtained in the present invention;
FIG. 5 is a schematic view of a Wollaston prism made from the crystal obtained by the present invention;
FIG. 6 is a schematic diagram of a wedge-shaped birefringent crystal polarizing beam splitter made of the crystal obtained in the present invention;
FIG. 7 is a schematic view of an optical isolator fabricated from the crystal of the present invention.
Detailed Description
Example 1
The aqueous solution cooling method is used for growing the large-size guanidino tetrafluoroborate birefringent crystal, and the specific operation is carried out according to the following steps:
a. according to the molar ratio of 1:2, commercially available guanidine carbonate and fluoroboric acid are mixed and reacted to generate a crude guanidino tetrafluoroborate product, and then recrystallization and drying are carried out to obtain high-purity guanidino tetrafluoroborate, and high-quality transparent guanidino tetrafluoroborate seed crystals with millimeter-sized particles are selected from the guanidino tetrafluoroborate seed crystals;
b. dissolving the guanidino tetrafluoroborate in the step a by using deionized water, and preparing a saturated solution at the temperature of 30 ℃;
c. transferring 100ml of the saturated solution in the step b to a crystal growth device by an aqueous solution cooling method, and then keeping the saturated solution at the saturation temperature of 30 ℃ for 24 hours;
d. b, fixing the guanidino tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then putting the seed crystal and the seed crystal frame into the crystal growth device in the step c to enable the seed crystal and the seed crystal frame to be positioned above the liquid level of the saturated solution; simultaneously, raising the temperature of the solution by 1 ℃ on the basis of the saturation temperature of 30 ℃, and preheating the seed crystals for 2 hours; then, completely immersing the seed crystal into the saturated solution, simultaneously cooling to a saturation temperature point, cooling at the speed of 0.01 ℃/day after the seed crystal reaches a growth equilibrium point, and keeping the rotation speed of the seed crystal at 5 revolutions per minute to carry out crystal growth;
e. after 60 days, a colorless, transparent 15X 10mm is obtained in a saturated solution in a crystal growth apparatus 3 And finally taking out the crystals from the saturated solution.
Example 2
The aqueous solution cooling method is used for growing the large-size guanidino tetrafluoroborate birefringent crystal, and the specific operation is carried out according to the following steps:
a. carrying out mixing reaction on commercially available guanidine carbonate and fluoroboric acid according to a molar ratio of 1:2 to generate a guanidyl tetrafluoroborate crude product, then carrying out recrystallization and drying to obtain high-purity guanidyl tetrafluoroborate, and selecting high-quality, transparent and millimeter-sized guanidyl tetrafluoroborate seed crystals from the guanidyl tetrafluoroborate crude product;
b. dissolving the guanidino tetrafluoroborate in the step a by using deionized water, and preparing a saturated solution at the temperature of 60 ℃;
c. transferring 1000ml of the saturated solution in the step b to an aqueous solution cooling method crystal growth device, and then keeping the saturated solution at the saturation temperature of 60 ℃ for 24 hours;
d. b, fixing the guanidino tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then putting the seed crystal and the seed crystal frame into the crystal growth device in the step c to enable the seed crystal and the seed crystal frame to be located above the liquid level of the saturated solution; simultaneously, raising the temperature of the solution by 5 ℃ on the basis of the saturation temperature of 60 ℃, and preheating the seed crystals for 24 hours; then, completely immersing the seed crystal into the saturated solution, simultaneously cooling to a saturation temperature point, cooling at a speed of 1 ℃/day after the seed crystal reaches a growth balance point, and keeping the rotation speed of the seed crystal at 50 revolutions per minute for crystal growth;
e. after 6 days, a colorless, transparent 52X 30mm is obtained in a saturated solution in a crystal growth apparatus 3 And finally taking out the crystals from the saturated solution.
Example 3
The aqueous solution cooling method is used for growing the large-size guanidino tetrafluoroborate birefringent crystal, and the specific operation is carried out according to the following steps:
a. carrying out mixing reaction on commercially available guanidine carbonate and fluoroboric acid according to a molar ratio of 1:2 to generate a guanidyl tetrafluoroborate crude product, then carrying out recrystallization and drying to obtain high-purity guanidyl tetrafluoroborate, and selecting high-quality, transparent and millimeter-sized guanidyl tetrafluoroborate seed crystals from the guanidyl tetrafluoroborate crude product;
b. dissolving the guanidino tetrafluoroborate in the step a by using deionized water, and preparing a saturated solution at the temperature of 30 ℃;
c. transferring 1000ml of the saturated solution in the step b to a crystal growth device of an aqueous solution cooling method, and then keeping the saturated solution at the saturation temperature of 30 ℃ for 24 hours;
d. b, fixing the guanidino tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then putting the seed crystal and the seed crystal frame into the crystal growth device in the step c to enable the seed crystal and the seed crystal frame to be positioned above the liquid level of the saturated solution; meanwhile, the temperature of the solution is raised by 1 ℃ on the basis of the saturation temperature of 30 ℃, and the seed crystals are preheated for 2 hours; then, completely immersing the seed crystal into the saturated solution, simultaneously cooling to a saturation temperature point, cooling at a speed of 0.01 ℃/day after the seed crystal reaches a growth balance point, and keeping the rotation speed of the seed crystal at 5 r/min for crystal growth;
e. through 6After 0 day, a colorless, transparent 45X 30mm was obtained in a saturated solution in a crystal growth apparatus 3 And finally taking out the crystals from the saturated solution.
Example 4
The aqueous solution cooling method is used for growing the large-size guanidino tetrafluoroborate birefringent crystal, and the specific operation is carried out according to the following steps:
a. carrying out mixing reaction on commercially available guanidine carbonate and fluoroboric acid according to a molar ratio of 1:2 to generate a guanidyl tetrafluoroborate crude product, then carrying out recrystallization and drying to obtain high-purity guanidyl tetrafluoroborate, and selecting high-quality, transparent and millimeter-sized guanidyl tetrafluoroborate seed crystals from the guanidyl tetrafluoroborate crude product;
b. dissolving the guanidino tetrafluoroborate in the step a by using deionized water, and preparing a saturated solution at the temperature of 35 ℃;
c. transferring 100ml of the saturated solution in the step b to an aqueous solution cooling method crystal growth device, and then keeping the saturated solution at the saturation temperature of 35 ℃ for 24 hours;
d. b, fixing the guanidino tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then putting the seed crystal and the seed crystal frame into the crystal growth device in the step c to enable the seed crystal and the seed crystal frame to be located above the liquid level of the saturated solution; meanwhile, raising the temperature of the solution by 2 ℃ on the basis of the saturation temperature of 35 ℃, and preheating the seed crystals for 12 hours; then, completely immersing the seed crystal into the saturated solution, simultaneously cooling to a saturation temperature point, cooling at the speed of 0.01 ℃/day after the seed crystal reaches a growth equilibrium point, and keeping the rotation speed of the seed crystal at 10 revolutions per minute to carry out crystal growth;
e. after 60 days, a colorless transparent 18X 16X 12mm is obtained in a saturated solution in a crystal growth apparatus 3 And finally taking the crystals out of the saturated solution.
Example 5
The aqueous solution cooling method is used for growing the large-size guanidino tetrafluoroborate birefringent crystal, and the specific operation is carried out according to the following steps:
a. carrying out mixing reaction on commercially available guanidine carbonate and fluoroboric acid according to a molar ratio of 1:2 to generate a guanidyl tetrafluoroborate crude product, then carrying out recrystallization and drying to obtain high-purity guanidyl tetrafluoroborate, and selecting high-quality, transparent and millimeter-sized guanidyl tetrafluoroborate seed crystals from the guanidyl tetrafluoroborate crude product;
b. dissolving the guanidino tetrafluoroborate in the step a by using deionized water, and preparing a saturated solution at the temperature of 60 ℃;
c. transferring 1000ml of the saturated solution in the step b to an aqueous solution cooling method crystal growth device, and then keeping the saturated solution at the saturation temperature of 60 ℃ for 24 hours;
d. b, fixing the guanidino tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then putting the seed crystal and the seed crystal frame into the crystal growth device in the step c to enable the seed crystal and the seed crystal frame to be positioned above the liquid level of the saturated solution; simultaneously, raising the temperature of the solution by 5 ℃ on the basis of the saturation temperature of 60 ℃, and preheating the seed crystals for 12 hours; then, completely immersing the seed crystal into the saturated solution, simultaneously cooling to a saturation temperature point, cooling at the speed of 1 ℃/day after the seed crystal reaches a growth balance point, and keeping the rotation speed of the seed crystal at 30 revolutions per minute to carry out crystal growth;
e. after 6 days, a colorless and transparent 28X 25X 18mm is obtained in a saturated solution in a crystal growth apparatus 3 And finally taking out the crystals from the saturated solution.
Example 6
The aqueous solution cooling method is used for growing the large-size guanidino tetrafluoroborate birefringent crystal, and the specific operation is carried out according to the following steps:
a. mixing commercially available guanidine carbonate and fluoroboric acid according to a molar ratio of 1:2 for reaction to generate a crude product of guanidino tetrafluoroborate, then recrystallizing and drying to obtain high-purity guanidino tetrafluoroborate, and selecting high-quality transparent guanidino tetrafluoroborate seed crystals with millimeter-level sizes from the guanidino tetrafluoroborate seed crystals;
b. dissolving the guanidino tetrafluoroborate in the step a by using deionized water, and preparing a saturated solution at the temperature of 45 ℃;
c. transferring 500ml of the saturated solution in the step b to an aqueous solution cooling method crystal growth device, and then keeping the saturated solution at the saturation temperature of 45 ℃ for 24 hours;
d. b, fixing the guanidino tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then putting the seed crystal and the seed crystal frame into the crystal growth device in the step c to enable the seed crystal and the seed crystal frame to be positioned above the liquid level of the saturated solution; meanwhile, raising the temperature of the solution by 2 ℃ on the basis of the saturation temperature of 45 ℃, and preheating the seed crystals for 12 hours; then, completely immersing the seed crystal into the saturated solution, simultaneously cooling to a saturation temperature point, cooling at the speed of 0.5 ℃/day after the seed crystal reaches a growth equilibrium point, and keeping the rotation speed of the seed crystal at 20 revolutions per minute to carry out crystal growth;
e. after 30 days, a colorless, transparent 35X 28X 25mm is obtained in a saturated solution in a crystal growth apparatus 3 And finally taking out the crystals from the saturated solution.
Example 7
The aqueous solution cooling method is used for growing the large-size guanidino tetrafluoroborate birefringent crystal, and the specific operation is carried out according to the following steps:
a. carrying out mixing reaction on commercially available guanidine carbonate and fluoroboric acid according to a molar ratio of 1:2 to generate a guanidyl tetrafluoroborate crude product, then carrying out recrystallization and drying to obtain high-purity guanidyl tetrafluoroborate, and selecting high-quality, transparent and millimeter-sized guanidyl tetrafluoroborate seed crystals from the guanidyl tetrafluoroborate crude product;
b. dissolving the guanidino tetrafluoroborate in the step a by using deionized water, and preparing a saturated solution at the temperature of 50 ℃;
c. transferring 800ml of the saturated solution in the step b to an aqueous solution cooling method crystal growth device, and then keeping the saturated solution at the saturation temperature of 50 ℃ for 24 hours;
d. b, fixing the guanidino tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then putting the seed crystal and the seed crystal frame into the crystal growth device in the step c to enable the seed crystal and the seed crystal frame to be positioned above the liquid level of the saturated solution; meanwhile, raising the temperature of the solution by 2 ℃ on the basis of the saturation temperature of 50 ℃, and preheating the seed crystals for 12 hours; then, completely immersing the seed crystal into the saturated solution, simultaneously cooling to a saturation temperature point, cooling at a speed of 0.1 ℃/day after the seed crystal reaches a growth balance point, and keeping the rotation speed of the seed crystal at 15 revolutions per minute for crystal growth;
e. after 40 days, a colorless and transparent 45X 30X 25mm is obtained in a saturated solution in a crystal growth apparatus 3 And finally taking out the crystals from the saturated solution.
Example 8
The aqueous solution cooling method is used for growing the large-size guanidino tetrafluoroborate birefringent crystal, and the specific operation is carried out according to the following steps:
a. mixing commercially available guanidine carbonate and fluoroboric acid according to a molar ratio of 1:2 for reaction to generate a crude product of guanidino tetrafluoroborate, then recrystallizing and drying to obtain high-purity guanidino tetrafluoroborate, and selecting high-quality transparent guanidino tetrafluoroborate seed crystals with millimeter-level sizes from the guanidino tetrafluoroborate seed crystals;
b. dissolving the guanidino tetrafluoroborate in the step a by using deionized water, and preparing a saturated solution at the temperature of 60 ℃;
c. transferring 1000ml of the saturated solution in the step b to an aqueous solution cooling method crystal growth device, and then keeping the saturated solution at the saturated temperature for 24 hours;
d. b, fixing the guanidino tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then putting the seed crystal and the seed crystal frame into the crystal growth device in the step c to enable the seed crystal and the seed crystal frame to be positioned above the liquid level of the saturated solution; simultaneously, raising the temperature of the solution by 2 ℃ on the basis of the saturation temperature of 60 ℃, and preheating the seed crystals for 12 hours; then, completely immersing the seed crystal into the saturated solution, simultaneously cooling to a saturation temperature point, cooling at the speed of 0.8 ℃/day after the seed crystal reaches a growth equilibrium point, and keeping the rotation speed of the seed crystal at 25 rpm to carry out crystal growth;
e. after 50 days, a colorless and transparent 58X 42X 36mm are obtained in a saturated solution in a crystal growth apparatus 3 And finally taking out the crystals from the saturated solution.
Example 9
The guanidino tetrafluoroborate birefringent crystal of the invention is used for manufacturing a Glan prism:
any of the guanidinium tetrafluoroborate birefringent crystals obtained in examples 1-8 was processed into two identical crystal prisms, as shown in fig. 4, with the light vertical incidence direction along the crystallographic axis of the crystal, the incidence plane containing two other crystallographic axes, and the two prisms were connected together along the inclined plane by a thin layer of air; or the connecting layer between the two prisms is changed into optical cement with different refractive indexes by air, so that polarizing prisms with different apex angle cutting are obtained, the prism design of 190-2450nm in a crystal light-transmitting wave band can be realized by adjusting the apex angle of the prisms, when a beam of light is incident perpendicular to an incident surface, the light directions of two beams of light with mutually perpendicular polarization directions do not generate deflection through the first prism of the Glan prism, and the incident angle on the inclined plane is equal to the included angle between the inclined plane of the prism and a right-angle plane (namely the apex angle of the prism). And selecting a proper vertex angle of the prism to enable one of the polarized lights to be totally reflected on the inclined plane, and emitting the other polarized light after passing through the connecting layers of the two prisms and the second prism.
Example 10
The guanidino tetrafluoroborate birefringent crystal of the invention is used for manufacturing a Wollaston prism:
two prisms were fabricated from any of the guanidino tetrafluoroborate birefringent crystals obtained in examples 1-8 and then bonded to form a wollaston prism as shown in fig. 5, wherein the apex angles of the two prisms were the same but the crystallographic axes included in the incident surface and the exit surface were different, the incident light was incident perpendicularly to the prism end surface, two polarized lights with mutually perpendicular polarization directions traveled in the same direction at different speeds in the first prism, when the light entered the second prism from the first prism, the refractive index was changed due to 90 degrees rotation of the crystallographic axis in the incident direction, the two polarized lights were separated by birefringence, respectively, and the two separated polarized lights were further separated by the second birefringence when they entered the air from the second prism, the larger the birefringence of the crystal, the more advantageous the separation of the light beams.
Example 11
The guanidino tetrafluoroborate birefringent crystal of the invention is used for manufacturing a polarization beam splitter:
the arbitrary guanidino tetrafluoroborate crystals obtained in examples 1 to 8 are used for preparing a wedge-shaped birefringent crystal polarization beam splitter (as shown in fig. 6), a wedge-shaped birefringent crystal passes through the direction along the y-axis direction of the crystal, a beam of natural light enters along the y-axis direction of the optical main axis and then is split into two beams of linearly polarized light through the crystal, and the larger the birefringence, the farther the two beams can be split, so that the beams can be separated conveniently.
Example 12
The guanidyl tetrafluoroborate crystal is used for manufacturing an optical isolator:
when any of the guanidino tetrafluoroborate birefringent crystals obtained in examples 1 to 8 is used for the production of an optical isolator, a Faraday rotator rotating the polarization plane of an incident beam by 45 ℃ is placed between a pair of birefringent crystal deflectors arranged to intersect each other by 45 ℃ to construct an optical isolator which allows only a forward propagating beam to pass through the system while blocking a backward propagating beam, FIG. 7a shows that the incident beam can pass through, and FIG. 7b shows that the reflected light is blocked.
Claims (6)
1. A large-size guanidyl tetrafluoroborate birefringent crystal is characterized in that the molecular formula of the crystal is as follows: CN 3 H 6 BF 4 Molecular weight of 146.90, belonging to trigonal system, and space group ofR3mCell parameter ofa = 7.4445(4) Å，b = 7.4445(4) Å，c = 9.1025(9) Å，α = 90.00°，β =90.00°，γ = 120.00°，Z = 3，V=436.88 (5); the crystal is grown by an aqueous solution cooling method, the transmission range of the crystal is 190-2450nm, and the birefringence is 0.12@546nm.
2. A method for growing large-size guanidino tetrafluoroborate birefringent crystal according to claim 1, wherein the method comprises the following steps:
a. carrying out mixing reaction on commercially available guanidine carbonate and fluoroboric acid according to a molar ratio of 1:2 to generate a guanidyl tetrafluoroborate crude product, then carrying out recrystallization and drying to obtain high-purity guanidyl tetrafluoroborate, and selecting high-quality, transparent and millimeter-sized guanidyl tetrafluoroborate seed crystals from the guanidyl tetrafluoroborate crude product;
b. dissolving the high-purity guanidino tetrafluoroborate obtained in the step a by using deionized water, and preparing a saturated solution at the temperature of 30-60 ℃;
c. transferring 100-1000ml of the saturated solution in the step b to a crystal growth device by an aqueous solution cooling method, and then keeping the saturated solution at the saturation temperature of 30-60 ℃ for 2-24 hours;
d. b, fixing the guanidino tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then putting the seed crystal and the seed crystal frame into the crystal growth device in the step c to enable the seed crystal and the seed crystal frame to be positioned above the liquid level of the saturated solution; simultaneously, raising the temperature of the solution by 1-5 ℃ on the basis of the saturation temperature of 30-60 ℃, and preheating the seed crystals for 2-24 hours; then, completely immersing the seed crystal into the saturated solution, simultaneously cooling to a saturation temperature point, cooling at the speed of 0.01-1 ℃/day after the seed crystal reaches a growth equilibrium point, and keeping the rotation speed of the seed crystal at 5-50 rpm to carry out crystal growth;
e. after 6-60 days, obtaining colorless and transparent centimeter-sized large-size guanidino tetrafluoroborate birefringent crystals in a saturated solution in a crystal growth device, and finally taking out the crystals from the saturated solution.
3. Use of a guanidinium tetrafluoroborate birefringent crystal of claim 1 in the preparation of a multiband polarizing beam splitting prism or optical element.
4. The use according to claim 3, wherein the polarizing beam splitter prism is a Glan prism, a Wollaston prism, a Rochon prism, a Nicole prism or a Saynmont prism.
5. Use according to claim 3, wherein the optical component is a polarizing beam splitter, an optical isolator, a circulator, a beam displacer, an optical polarizer, an optical analyzer, an optical polarizer, an optical modulator, a polarizing beam splitter, a phase retarder device or an electro-optical modulator device.
6. The use according to claim 3, wherein the polarizing beam splitter prism or the optical element is made for a plurality of bands of infrared-visible-ultraviolet-deep ultraviolet.
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