CN115874289B - Large-size guanidyl tetrafluoroborate birefringent crystal, and growth method and application thereof - Google Patents
Large-size guanidyl tetrafluoroborate birefringent crystal, and growth method and application thereof Download PDFInfo
- Publication number
- CN115874289B CN115874289B CN202211670253.0A CN202211670253A CN115874289B CN 115874289 B CN115874289 B CN 115874289B CN 202211670253 A CN202211670253 A CN 202211670253A CN 115874289 B CN115874289 B CN 115874289B
- Authority
- CN
- China
- Prior art keywords
- crystal
- tetrafluoroborate
- prism
- guanidyl
- seed crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to a large-size guanidyl tetrafluoroborate birefringent crystal, a growing method and application thereof, wherein the crystal has a molecular formula of CN 3H6BF4, a molecular weight of 146.90, belongs to a trigonal system, a space group of R3m, a unit cell parameter of a= 7.4445 (4) a, b= 7.4445 (4) a, c= 9.1025 (9) a, a=90.00 degrees, beta=90.00 degrees, gamma=120.00 degrees, Z=3, V= 436.88 (5); the transmission range of the crystal is 190-2450 nm, the double refractive index is 0.12@546 nm, and the crystal is grown by adopting an aqueous solution cooling method. The crystal has larger double refractive index and wide transmission range, is easy to grow and process, and can be used as double refractive crystal. The crystal is used for manufacturing a polarization beam splitter prism or an optical element of an infrared-visible-ultraviolet-deep ultraviolet band, and the like, and has important application in the aspects of manufacturing an optical beam splitter prism such as a gram prism, a Rochon prism, a nicol prism, a Wollaston prism, a Saunamont prism, a beam splitter, an optical isolator, a circulator, a beam shifter, a polarizer, an analyzer, an optical polarizer, a phase delay device, an electro-optic modulation device, and the like.
Description
Technical Field
The invention relates to a growth method and application of a large-size guanidinium tetrafluoroborate crystal with a molecular formula of CN 3H6BF4 for an infrared-visible-ultraviolet-deep ultraviolet band, belonging to the technical field of crystal materials and the technical field of optics.
Background
When a light beam is incident on an anisotropic crystal material, a phenomenon of being split into two light beams and refracted in different directions is called a birefringence phenomenon, and the two light beams generated by the birefringence are linearly polarized light with the polarization directions being perpendicular to each other. With the continuous expansion of the breadth and depth of laser application and the rapid development of optical communication technology, birefringent crystals have become an indispensable important material for modulating the polarization state of light. Currently, birefringent crystals are key materials for manufacturing polarizing beam splitters such as a graham prism and a wollaston prism, and optical communication elements such as an optical isolator, a beam shifter and a circulator. A commonly practiced birefringent crystal is required to have as large a birefringence as possible in the operating band.
The birefringent optical crystal has important application value in various fields such as scientific research, traffic, national defense, industry and the like, and along with the rapid development of laser industry and industry, the search for a new birefringent material with good performance is urgent. The common birefringent materials are mainly 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 performance, but because of the high melting point of YVO 4, an iridium crucible is required to be used for carrying out pulling growth, and the growth atmosphere is a weak oxygen atmosphere, so that the problem of valence change of iridium element exists during growth, the quality of the crystal is reduced, and high-quality crystal is not easy to obtain; alpha-BaB 2O4 (alpha-BBO) is easily cracked during crystal growth due to the existence of solid phase transition; liNbO 3 crystals are easy to obtain large-size crystals, but the birefringence is too small; calcite crystal mainly exists in a natural form, is difficult to artificially synthesize, has smaller general size and higher impurity content, cannot meet the requirements of large-size optical polarizing elements, is easy to dissociate, is difficult to process, and has low crystal utilization rate. In view of this, it is highly necessary to find a birefringent crystal having a large birefringence, good and stable overall performance parameters, and at the same time, easy to grow a bulk crystal of good quality and large size.
Guanidine tetrafluoroborate (CN 3H6BF4) has been reported since the eighties of the last century. In 1987, a.kozak et al studied the crystal structure of guanidinium tetrafluoroborate (a.kozak, et al 1987,J.Phys.C:Solid State Phys, 20,5433); thermoelectric, dielectric, piezoelectric and elastic properties of guanidinium tetrafluoroborate crystals were studied by S.Haussuhl in 1989 (S.Haussuhl, 1989, Z.Kristalogr., 187,153); in 2018, S.Nandhini et al have conducted studies of structural, optical, mechanical, electrical, and nonlinear optics (S.Nandhini et al 2018,Optics and Laser Technology,105,249). The existing crystal growth methods adopted in the literature are all slow evaporation methods, and no aqueous solution cooling method growth method is reported, and no application or research report related to the method as birefringent crystal is available. The growth method of the guanidyl tetrafluoroborate birefringent crystal is an aqueous solution cooling method, and the guanidyl tetrafluoroborate birefringent crystal is used as a birefringent crystal for preparing a multiband polarization beam splitter prism or an optical element.
Disclosure of Invention
The invention aims to provide a large-size guanidyl tetrafluoroborate birefringent crystal, which has a molecular formula of CN 3H6BF4, a molecular weight of 146.90, belongs to a trigonal system, has a space group of R3m and has a unit cell parameter of Α=90.00 °, β=90.00 °, γ=120.00 °, z=3, v= 436.88 (5); has wide light transmission wave band, the transmission range is 190-2450nm, and the double refraction index is 0.12@546nm.
It is another object of the present invention to provide a method for growing large-sized guanidyl tetrafluoroborate birefringent crystal in aqueous solution.
It is still another object of the present invention to provide a use of large-sized guanidinium tetrafluoroborate birefringent crystal as birefringent crystal.
The invention relates to a large-size guanidinium tetrafluoroborate birefringent crystal, which has the following molecular formula: CN 3H6BF4, molecular weight 146.90, which belongs to trigonal system, space group R3m, unit cell parameter Α=90.00 °, β=90.00 °, γ=120.00 °, z=3, v= 436.88 (5); the crystal is grown by adopting an aqueous solution cooling method, the transmission range of the crystal is 190-2450nm, and the double refractive index is 0.12@546nm.
The method for growing the large-size guanidyl tetrafluoroborate birefringent crystal adopts an aqueous solution cooling method to grow the crystal, and comprises the following specific operations:
a. Mixing commercially available guanidine carbonate and fluoboric acid according to a molar ratio of 1:2 to generate a coarse product of the guanidyl tetrafluoroborate, then recrystallizing and drying to obtain high-purity guanidyl tetrafluoroborate, and selecting high-quality transparent guanidyl tetrafluoroborate seed crystals with millimeter-sized dimensions from the high-purity guanidyl tetrafluoroborate seed crystals;
b. Dissolving the high-purity guanidyl tetrafluoroborate obtained in the step a by 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 into an aqueous solution cooling method crystal growth device, and then keeping the saturated solution at the saturated temperature of 30-60 ℃ for 2-24 hours;
d. C, fixing the guanidinium tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then placing 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, the temperature of the solution is increased by 1 to 5 ℃ on the basis of the saturation temperature of 30 to 60 ℃ and the seed crystal is preheated for 2 to 24 hours; then immersing the seed crystal into saturated solution, cooling to saturation temperature point, cooling at 0.01-1 deg.C/day after the seed crystal reaches growth balance point, maintaining the rotation speed of seed crystal at 5-50 rpm, and growing crystal;
e. after 6-60 days, colorless transparent large-size guanidyl tetrafluoroborate birefringent crystal with centimeter level is obtained in saturated solution in a crystal growth device, and finally the crystal is taken out from the saturated solution.
The use of said guanidinium tetrafluoroborate birefringent crystal for the preparation of a multiband polarizing beam splitter prism or optical element.
The polarization beam splitting prism is a gram prism, a Wollaston prism, a Rochon prism, a Nicole prism or a Saunamont prism.
The optical element is a polarized light beam splitter, an optical isolator, a circulator, a light beam shifter, an optical polarizer, an optical analyzer, an optical polarizer, an optical modulator, a polarized light 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 used crystal growth device is a self-made water bath.
The guanidyl tetrafluoroborate birefringent crystal has the characteristics of 190-2450nm of light transmission range, 0.12@546nm of birefringence, 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 in infrared-visible-ultraviolet-deep ultraviolet wave bands.
The method for growing the guanidyl tetrafluoroborate birefringent crystal has the advantages that the guanidyl tetrafluoroborate crystal with the large size of centimeter grade is obtained by the method, the crystal has no lamellar growth habit, the crystal is easy to grow and transparent and has no package in the growth process of the crystal, the growth speed is high, the energy consumption is low, the cost is low, the large-size crystal is easy to obtain, and the like.
The guanidinium tetrafluoroborate birefringent crystal grown by the growth method of the invention is characterized in that crystal blanks are oriented according to crystallographic data of the crystal, the crystal is cut according to required angles, thickness and section size, and the light-passing surface of the crystal is polished, thus the crystal can be used as a polarization beam splitter prism or an optical element.
Drawings
FIG. 1 is a block diagram of a guanidinium tetrafluoroborate crystal according to the present invention: wherein (a) an X-ray diffraction pattern (b) is a spatial structure;
FIG. 2 is a photograph of a guanidine tetrafluoroborate crystal according to the present invention;
FIG. 3 is a prism photograph of the present invention for measuring refractive index of guanidinium tetrafluoroborate crystals;
FIG. 4 is a schematic view of a gram prism made of the crystal of the present invention;
FIG. 5 is a schematic view of a Wollaston prism made of the crystal of the present invention;
FIG. 6 is a schematic diagram of a wedge-shaped birefringent crystal polarizing beam splitter made from the crystals of the present invention;
FIG. 7 is a schematic diagram of an optical isolator made from the crystals obtained in the present invention.
Detailed Description
Example 1
The aqueous solution cooling method is used for growing large-size guanidyl tetrafluoroborate birefringent crystals, and the specific operation is carried out according to the following steps:
a. mixing commercially available guanidine carbonate and fluoboric acid according to a molar ratio of 1:2 to generate a coarse product of the guanidyl tetrafluoroborate, then recrystallizing and drying to obtain high-purity guanidyl tetrafluoroborate, and selecting high-quality transparent guanidyl tetrafluoroborate seed crystals with millimeter-sized dimensions from the high-purity guanidyl tetrafluoroborate seed crystals;
b. dissolving the guanidinium tetrafluoroborate in the step a by deionized water, and preparing a saturated solution at the temperature of 30 ℃;
c. Transferring 100ml of the saturated solution in the step b into an aqueous solution cooling method crystal growth device, and then keeping the saturated solution at the saturation temperature of 30 ℃ for 24 hours;
d. C, fixing the guanidinium tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then placing 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 increased by 1 ℃ on the basis of the saturation temperature of 30 ℃ and the seed crystal is preheated for 2 hours; then, the seed crystal is completely immersed into the saturated solution, the temperature is reduced to a saturation temperature point, the temperature is reduced at a speed of 0.01 ℃/day after the seed crystal reaches a growth balance point, the rotation speed of the seed crystal is kept to be 5 revolutions per minute, and crystal growth is carried out;
e. After 60 days, a colorless transparent 15×15×10mm 3 large-size guanidinium tetrafluoroborate crystal was obtained in a saturated solution in a crystal growth apparatus, and finally the crystal was taken out of the saturated solution.
Example 2
The aqueous solution cooling method is used for growing large-size guanidyl tetrafluoroborate birefringent crystals, and the specific operation is carried out according to the following steps:
a. Mixing commercially available guanidine carbonate and fluoboric acid according to a molar ratio of 1:2 to generate a coarse product of the guanidyl tetrafluoroborate, then recrystallizing and drying to obtain high-purity guanidyl tetrafluoroborate, and selecting high-quality transparent guanidyl tetrafluoroborate seed crystals with millimeter-sized dimensions from the high-purity guanidyl tetrafluoroborate seed crystals;
b. dissolving the guanidinium tetrafluoroborate in the step a by deionized water, and preparing a saturated solution at the temperature of 60 ℃;
c. transferring 1000ml of the saturated solution in the step b into an aqueous solution cooling method crystal growth device, and then keeping the saturated solution at the saturated temperature of 60 ℃ for 24 hours;
d. c, fixing the guanidinium tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then placing 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, the temperature of the solution is raised by 5 ℃ on the basis of the saturation temperature of 60 ℃ and the seed crystal is preheated for 24 hours; then, completely immersing the seed crystal into a 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, keeping the rotation speed of the seed crystal at 50 rpm, and carrying out crystal growth;
e. After 6 days, a colorless transparent large-size 52×52×30mm 3 guanidinium tetrafluoroborate crystal was obtained in a saturated solution in a crystal growth apparatus, and finally the crystal was taken out of the saturated solution.
Example 3
The aqueous solution cooling method is used for growing large-size guanidyl tetrafluoroborate birefringent crystals, and the specific operation is carried out according to the following steps:
a. Mixing commercially available guanidine carbonate and fluoboric acid according to a molar ratio of 1:2 to generate a coarse product of the guanidyl tetrafluoroborate, then recrystallizing and drying to obtain high-purity guanidyl tetrafluoroborate, and selecting high-quality transparent guanidyl tetrafluoroborate seed crystals with millimeter-sized dimensions from the high-purity guanidyl tetrafluoroborate seed crystals;
b. dissolving the guanidinium tetrafluoroborate in the step a by 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 by an aqueous solution cooling method, and then keeping the saturated solution at the saturation temperature of 30 ℃ for 24 hours;
d. C, fixing the guanidinium tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then placing 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 increased by 1 ℃ on the basis of the saturation temperature of 30 ℃ and the seed crystal is preheated for 2 hours; then, the seed crystal is completely immersed into the saturated solution, the temperature is reduced to a saturation temperature point, the temperature is reduced at a speed of 0.01 ℃/day after the seed crystal reaches a growth balance point, the rotation speed of the seed crystal is kept to be 5 revolutions per minute, and crystal growth is carried out;
e. After 60 days, a colorless transparent large-size 45×45×30mm 3 guanidinium tetrafluoroborate crystal was obtained in a saturated solution in a crystal growth apparatus, and finally the crystal was taken out of the saturated solution.
Example 4
The aqueous solution cooling method is used for growing large-size guanidyl tetrafluoroborate birefringent crystals, and the specific operation is carried out according to the following steps:
a. Mixing commercially available guanidine carbonate and fluoboric acid according to a molar ratio of 1:2 to generate a coarse product of the guanidyl tetrafluoroborate, then recrystallizing and drying to obtain high-purity guanidyl tetrafluoroborate, and selecting high-quality transparent guanidyl tetrafluoroborate seed crystals with millimeter-sized dimensions from the high-purity guanidyl tetrafluoroborate seed crystals;
b. Dissolving the guanidinium tetrafluoroborate in the step a by deionized water, and preparing a saturated solution at the temperature of 35 ℃;
c. transferring 100ml of the saturated solution in the step b into an aqueous solution cooling method crystal growth device, and then keeping the saturated solution at the saturated temperature of 35 ℃ for 24 hours;
d. C, fixing the guanidinium tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then placing 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 increased by 2 ℃ on the basis of the saturation temperature of 35 ℃ and the seed crystal is preheated for 12 hours; then, the seed crystal is completely immersed into the saturated solution, the temperature is reduced to a saturation temperature point, the temperature is reduced at the speed of 0.01 ℃/day after the seed crystal reaches a growth balance point, the rotation speed of the seed crystal is kept to be 10 revolutions per minute, and crystal growth is carried out;
e. After 60 days, a colorless transparent 18×16×12mm 3 large-size guanidinium tetrafluoroborate crystal was obtained in a saturated solution in a crystal growth apparatus, and finally the crystal was taken out of the saturated solution.
Example 5
The aqueous solution cooling method is used for growing large-size guanidyl tetrafluoroborate birefringent crystals, and the specific operation is carried out according to the following steps:
a. Mixing commercially available guanidine carbonate and fluoboric acid according to a molar ratio of 1:2 to generate a coarse product of the guanidyl tetrafluoroborate, then recrystallizing and drying to obtain high-purity guanidyl tetrafluoroborate, and selecting high-quality transparent guanidyl tetrafluoroborate seed crystals with millimeter-sized dimensions from the high-purity guanidyl tetrafluoroborate seed crystals;
b. Dissolving the guanidinium tetrafluoroborate in the step a by deionized water, and preparing a saturated solution at the temperature of 60 ℃;
c. transferring 1000ml of the saturated solution in the step b into an aqueous solution cooling method crystal growth device, and then keeping the saturated solution at the saturated temperature of 60 ℃ for 24 hours;
d. C, fixing the guanidinium tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then placing 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, the temperature of the solution is raised by 5 ℃ on the basis of the saturation temperature of 60 ℃ and the seed crystal is preheated for 12 hours; then, completely immersing the seed crystal into a 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, keeping the rotation speed of the seed crystal at 30 revolutions per minute, and carrying out crystal growth;
e. after 6 days, colorless transparent 28×25×18mm 3 large-size guanidinium tetrafluoroborate crystals were obtained in a saturated solution in a crystal growth apparatus, and finally the crystals were removed from the saturated solution.
Example 6
The aqueous solution cooling method is used for growing large-size guanidyl tetrafluoroborate birefringent crystals, and the specific operation is carried out according to the following steps:
a. Mixing commercially available guanidine carbonate and fluoboric acid according to a molar ratio of 1:2 to generate a coarse product of the guanidyl tetrafluoroborate, then recrystallizing and drying to obtain high-purity guanidyl tetrafluoroborate, and selecting high-quality transparent guanidyl tetrafluoroborate seed crystals with millimeter-sized dimensions from the high-purity guanidyl tetrafluoroborate seed crystals;
b. Dissolving the guanidinium tetrafluoroborate in the step a by deionized water, and preparing a saturated solution at the temperature of 45 ℃;
c. Transferring 500ml of the saturated solution in the step b into an aqueous solution cooling method crystal growth device, and then keeping the saturated solution at 45 ℃ for 24 hours;
d. C, fixing the guanidinium tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then placing 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 increased by 2 ℃ on the basis of the saturation temperature of 45 ℃ and the seed crystal is preheated for 12 hours; then, the seed crystal is completely immersed into the saturated solution, the temperature is reduced to a saturation temperature point, the temperature is reduced at the speed of 0.5 ℃/day after the seed crystal reaches a growth balance point, the rotation speed of the seed crystal is kept to be 20 revolutions per minute, and crystal growth is carried out;
e. After 30 days, a colorless transparent large-size guanidyl tetrafluoroborate crystal of 35×28×25mm 3 was obtained in a saturated solution in a crystal growth apparatus, and finally the crystal was taken out of the saturated solution.
Example 7
The aqueous solution cooling method is used for growing large-size guanidyl tetrafluoroborate birefringent crystals, and the specific operation is carried out according to the following steps:
a. Mixing commercially available guanidine carbonate and fluoboric acid according to a molar ratio of 1:2 to generate a coarse product of the guanidyl tetrafluoroborate, then recrystallizing and drying to obtain high-purity guanidyl tetrafluoroborate, and selecting high-quality transparent guanidyl tetrafluoroborate seed crystals with millimeter-sized dimensions from the high-purity guanidyl tetrafluoroborate seed crystals;
b. dissolving the guanidinium tetrafluoroborate in the step a by deionized water and preparing a saturated solution at the temperature of 50 ℃;
c. Transferring 800ml of the saturated solution in the step b into an aqueous solution cooling method crystal growth device, and then keeping the saturated solution at the saturated temperature of 50 ℃ for 24 hours;
d. C, fixing the guanidinium tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then placing 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 increased by 2 ℃ on the basis of the saturation temperature of 50 ℃ and the seed crystal is preheated for 12 hours; then, the seed crystal is completely immersed into the saturated solution, the temperature is reduced to a saturation temperature point, the temperature is reduced at the speed of 0.1 ℃/day after the seed crystal reaches a growth balance point, the rotation speed of the seed crystal is kept to be 15 revolutions per minute, and crystal growth is carried out;
e. After 40 days, a colorless transparent large-size 45×30×25mm 3 guanidinium tetrafluoroborate crystal was obtained in a saturated solution in a crystal growth apparatus, and finally the crystal was taken out of the saturated solution.
Example 8
The aqueous solution cooling method is used for growing large-size guanidyl tetrafluoroborate birefringent crystals, and the specific operation is carried out according to the following steps:
a. Mixing commercially available guanidine carbonate and fluoboric acid according to a molar ratio of 1:2 to generate a coarse product of the guanidyl tetrafluoroborate, then recrystallizing and drying to obtain high-purity guanidyl tetrafluoroborate, and selecting high-quality transparent guanidyl tetrafluoroborate seed crystals with millimeter-sized dimensions from the high-purity guanidyl tetrafluoroborate seed crystals;
b. Dissolving the guanidinium tetrafluoroborate in the step a by deionized water, and preparing a saturated solution at the temperature of 60 ℃;
c. transferring 1000ml of the saturated solution in the step b into an aqueous solution cooling method crystal growth device, and then keeping the saturated solution at a saturation temperature for 24 hours;
d. C, fixing the guanidinium tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then placing 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, the temperature of the solution is increased by 2 ℃ on the basis of the saturation temperature of 60 ℃ and the seed crystal is preheated for 12 hours; then, the seed crystal is completely immersed into the saturated solution, the temperature is reduced to a saturation temperature point, the temperature is reduced at the speed of 0.8 ℃/day after the seed crystal reaches a growth balance point, the rotation speed of the seed crystal is kept to be 25 revolutions per minute, and crystal growth is carried out;
e. After 50 days, a colorless transparent 58×42×36mm 3 large-size guanidinium tetrafluoroborate crystal was obtained in a saturated solution in a crystal growth apparatus, and finally the crystal was taken out of the saturated solution.
Example 9
Gram type prisms were made using the guanidinium tetrafluoroborate birefringent crystal of the present invention:
Processing any guanidine tetrafluoroborate birefringent crystal obtained in examples 1-8 into two identical crystal prisms, wherein the vertical incidence direction of light is along the crystallographic axis of the crystal as shown in fig. 4, the incidence plane comprises two other crystallographic axes, and the two prisms are connected together along the inclined plane through an air thin layer; or the connecting layer between two prisms is changed into optical cement with different refractive indexes by air, so that polarized prisms cut by different vertex angles are obtained, the prism design of 190-2450nm in a crystal light transmission band can be realized by adjusting the vertex angle of the prism, when one beam of light is incident perpendicularly to an incident surface, the two beams of light with mutually perpendicular polarization directions do not deviate through the first prism of the gram prism, and the incident angle on the inclined surface is equal to the included angle between the inclined surface of the prism and the right-angle surface (namely the vertex angle of the prism). And selecting proper prism vertex angles to enable one beam of polarized light to be totally reflected on the inclined plane, and the other beam of polarized light to be emitted after passing through the connecting layer of the two prisms and the second prism.
Example 10
Wollaston prism is made of guanidine tetrafluoroborate birefringent crystal of the present invention:
Any of the guanidinium tetrafluoroborate birefringent crystals obtained in examples 1-8 were processed into two prisms and then bonded to form a Wollaston prism, as shown in fig. 5, the apex angles of the two prisms were the same but the incident plane and the exit plane contained crystallographic axes were different, the incident light was perpendicularly incident on the prism end face, in prism one, two polarized light beams having mutually perpendicular polarization directions traveled in the same direction at different speeds, when light entered prism two from prism one, the refractive index was changed due to the 90 degrees rotation of the crystallographic axes in the incident direction, the two linearly polarized light beams were separated due to the respective birefringence, and the two separated polarized light beams were further separated due to the second birefringence when the two polarized light beams entered air from prism two, the greater the birefringence of the crystal was, the more advantageous for the separation of the light beams.
Example 11
Polarizing beam splitters were made using the guanidinium tetrafluoroborate birefringent crystal of the present invention:
Any of the guanidinium tetrafluoroborate crystals obtained in examples 1-8 was used to prepare a wedge-shaped birefringent crystal polarizing beam splitter (as shown in fig. 6), a wedge-shaped birefringent crystal, through which a natural light beam was incident in the y-axis direction of the optical principal axis and then split into two linearly polarized light beams by the crystal, the greater the birefringence, the farther the two light beams were split, facilitating the splitting of the light beams.
Example 12
Optical isolators were made using the guanidinium tetrafluoroborate crystals of the present invention:
By placing any of the guanidinium tetrafluoroborate birefringent crystals obtained in examples 1-8 between a pair of birefringent crystal deflectors placed at 45 ° intersections of each other with a faraday rotator having a 45 ° rotation of the plane of polarization of the incident beam, an optical isolator can be constructed which allows only forward propagating light beams to pass through the system while blocking back propagating light beams, and figure 7a shows that the incident beam can pass through and figure 7b shows that the reflected light is blocked.
Claims (6)
1. A large-size guanidine tetrafluoroborate birefringent crystal is characterized in that the molecular formula of the crystal is: CN 3H6BF4, molecular weight 146.90, belonging to trigonal system, space group R3m, unit cell parameters a= 7.4445 (4) a, b= 7.4445 (4) a, c= 9.1025 (9) a, α=90.00°, β=90.00°, γ=120.00°, z=3, v= 436.88 (5); the crystal is grown by adopting an aqueous solution cooling method, the transmission range of the crystal is 190-2450 nm, and the double refraction index is 0.12@546 nm.
2. A method for growing large-size guanidinium tetrafluoroborate birefringent crystals according to claim 1, wherein the method comprises the following steps:
a. Mixing commercially available guanidine carbonate and fluoboric acid according to a molar ratio of 1:2 to generate a coarse product of the guanidyl tetrafluoroborate, then recrystallizing and drying to obtain high-purity guanidyl tetrafluoroborate, and selecting high-quality transparent guanidyl tetrafluoroborate seed crystals with millimeter-sized dimensions from the high-purity guanidyl tetrafluoroborate seed crystals;
b. Dissolving the high-purity guanidyl tetrafluoroborate obtained in the step a by 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 into an aqueous solution cooling method crystal growth device, and then keeping the saturated solution at the saturated temperature of 30-60 ℃ for 2-24 hours;
d. C, fixing the guanidinium tetrafluoroborate seed crystal selected in the step a on a seed crystal frame, and then placing 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, the temperature of the solution is increased by 1 to 5 ℃ on the basis of the saturation temperature of 30 to 60 ℃ and the seed crystal is preheated for 2 to 24 hours; then immersing the seed crystal into saturated solution, cooling to saturation temperature point, cooling at 0.01-1 deg.C/day after the seed crystal reaches growth balance point, maintaining the rotation speed of seed crystal at 5-50 rpm, and growing crystal;
e. after 6-60 days, colorless transparent large-size guanidyl tetrafluoroborate birefringent crystal with centimeter level is obtained in saturated solution in a crystal growth device, and finally the crystal is taken out from the saturated solution.
3. Use of a guanidinium tetrafluoroborate birefringent crystal according to claim 1 in the manufacture of a multiband polarizing beam splitting prism or optical element.
4. A use according to claim 3, wherein the polarizing beam splitter prism is a gram prism, a wollaston prism, a rochon prism, a nicol prism or a senor monte prism.
5. The use according to claim 3, wherein the optical element is a polarizing beam splitter, an optical isolator, a circulator, a beam shifter, an optical polarizer, an optical analyzer, an optical polarizer, an optical modulator, a polarizing beam splitter, a phase delay device or an electro-optical modulation device.
6. Use according to claim 3, characterized in that a polarizing beam splitter prism or optical element is produced for a plurality of infrared-visible-ultraviolet-deep ultraviolet bands.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211670253.0A CN115874289B (en) | 2022-12-24 | 2022-12-24 | Large-size guanidyl tetrafluoroborate birefringent crystal, and growth method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211670253.0A CN115874289B (en) | 2022-12-24 | 2022-12-24 | Large-size guanidyl tetrafluoroborate birefringent crystal, and growth method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115874289A CN115874289A (en) | 2023-03-31 |
| CN115874289B true CN115874289B (en) | 2024-11-15 |
Family
ID=85755494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211670253.0A Active CN115874289B (en) | 2022-12-24 | 2022-12-24 | Large-size guanidyl tetrafluoroborate birefringent crystal, and growth method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115874289B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112760717A (en) * | 2020-12-26 | 2021-05-07 | 中国科学院新疆理化技术研究所 | Guanidine tetrafluoroborate nonlinear optical crystal, preparation method and application |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839421B (en) * | 2011-06-21 | 2015-06-10 | 中国科学院理化技术研究所 | Borate birefringent crystal for ultraviolet deep ultraviolet, and growth method and application thereof |
| CN103849932B (en) * | 2014-03-13 | 2016-08-24 | 中国科学院理化技术研究所 | Barium sodium fluoborate ultraviolet birefringent crystal, and growth method and application thereof |
| CN108070902B (en) * | 2016-11-15 | 2019-11-22 | 中国科学院新疆理化技术研究所 | Compound sodium fluoroborate and sodium fluoroborate birefringent crystal, preparation method and use |
| CN106521628B (en) * | 2016-12-01 | 2021-05-25 | 新疆大学 | Lead fluorovanadate birefringent crystal and preparation method and application thereof |
| CN113773231B (en) * | 2021-09-13 | 2023-03-21 | 中国科学院新疆理化技术研究所 | Compound hydroxyl guanidine tetrafluoroborate and hydroxyl guanidine tetrafluoroborate nonlinear optical crystal, preparation method and application |
-
2022
- 2022-12-24 CN CN202211670253.0A patent/CN115874289B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112760717A (en) * | 2020-12-26 | 2021-05-07 | 中国科学院新疆理化技术研究所 | Guanidine tetrafluoroborate nonlinear optical crystal, preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| Achieving the full-wavelength phase-matching for efficient nonlinear optical frequency conversion in C(NH2)3BF4;Pan, SL等;NATURE PHOTONICS;20230612;第17卷(第8期);694–701 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115874289A (en) | 2023-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9360610B2 (en) | Borate birefringent crystal applicable to ultraviolet (UV) or deep ultraviolet (DUV) range, and growth method and use thereof | |
| CN103074684B (en) | Borate birefringent crystal for ultraviolet band, and growth method and application thereof | |
| US11898268B2 (en) | Calcium metaborate birefringent crystal, preparation method and use thereof | |
| CN101323981B (en) | Use of birefraction borate crystal | |
| CN108070902A (en) | Compound sodium fluoborate and sodium fluoborate birefringece crystal and preparation method and purposes | |
| CN106917140A (en) | Boronic acid compound lithium sodium birefringece crystal and preparation method and purposes | |
| CN111945228B (en) | A kind of birefringent crystal material, its preparation method and use | |
| CN110618476A (en) | Application of tin boron oxygen chlorine birefringent crystal | |
| US20160305041A1 (en) | Preparation method and application of sodium barium fluoroborate birefringent crystal | |
| US10604863B2 (en) | Lithium metaborate crystal, preparation method and use thereof | |
| CN115874289B (en) | Large-size guanidyl tetrafluoroborate birefringent crystal, and growth method and application thereof | |
| CN108425152B (en) | Strontium metaborate birefringent crystal, preparation method and application thereof | |
| CN106192006A (en) | Compound lithium vanadate sodium optical crystal and its production and use | |
| CN106192001B (en) | Caesium lead carbon oxygen iodine birefringece crystal and preparation method and purposes | |
| CN111593406A (en) | Compound tin boron oxy bromide and tin boron oxy bromide birefringent crystal and preparation method and use | |
| CN106521628B (en) | Lead fluorovanadate birefringent crystal and preparation method and application thereof | |
| CN102586878B (en) | Compound of barium bismuth boron oxygen and compound of barium bismuth boron oxygen optical crystal and its production and use | |
| CN112505816A (en) | Compound potassium barium borate, potassium barium borate birefringent crystal, preparation method and application | |
| CN116283532A (en) | Compound hydrated lithium hydrogen squarylate and hydrated lithium hydrogen squarylate birefringent crystal, preparation method and use | |
| CN114481321B (en) | Electro-optic crystal potassium boroniobate and application thereof | |
| CN105568381A (en) | Yttrium phosphate double-refraction crystal and growing method and application thereof | |
| CN119684164B (en) | Compound calcium guanidine nitrate and calcium guanidine nitrate birefringent crystal, and preparation method and application thereof | |
| CN106811795B (en) | Preparation method and application of lithium borate birefringent crystal | |
| CN120556143A (en) | Compound lanthanum barium antimony sulfide and lanthanum barium antimony sulfide mid- and far-infrared birefringent optical crystals and their preparation method and application | |
| CN119192234B (en) | Ammonium aminomethylphosphonate compound, birefringent crystal thereof, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |