CN105316764B - One water monohydroxy of compound, five line borate nonlinear optical crystal and preparation method and purposes - Google Patents
One water monohydroxy of compound, five line borate nonlinear optical crystal and preparation method and purposes Download PDFInfo
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Abstract
The present invention relates to a kind of one water monohydroxy of compound, five line borate nonlinear optical crystal and preparation method and purposes, which is Ca2B5O9OH·H2O, molecular weight 313.23, crystal belong to monoclinic system, space groupCc, cell parameter is a=10.780 (3), b=6.5110 (19), c=12.339 (4),β=115.057 (19) °, V=784.6 (4)3.Using hydro-thermal method, one water monohydroxy of compound, five line borate nonlinear optical crystal is obtained by the method for program cooling or Temperature fall, its powder SHG effect of the crystal is about KDP (KH2PO4) 2 times, its ultraviolet cut-on side can be used as deep ultraviolet nonlinear optical crystal in 190 below nm.The crystal has the advantages that easy to operate, cost is low, and material toxicity is low, and growth cycle is short, and physico-chemical property is stablized.Prepare times frequency generator, on be used widely in the device for non-linear optical such as frequency converter, lower frequency converter or optical parametric oscillator.
Description
Technical field
The present invention relates to one water monohydroxy of compound, five line borate nonlinear optical crystal and preparation method and purposes, the crystalline substance
The chemical formula of body is Ca2B5O9OH·H2O, the device for non-linear optical made using the crystal.The invention belongs to inorganic chemistry neck
Domain, falls within materials science field and optical field.
Background technology
1961, Franken was found that quartz crystal laser freuqency doubling phenomenon first, and the discovery of the phenomenon, not only indicates
The birth of nonlinear optics, and effectively promote developing rapidly for non-linear optical crystal material.Therefore, nonlinear optics is
The subject risen afterwards is produced after laser, it belongs to a branch of photoelectronics, corresponding nonlinear optical crystal material
Material is an important component of photoelectric material.With the further investigation of nonlinear optics and the continuous development of new material,
Non-linear optical crystal material is in Solid State Laser technology, infrared technique, optical communication technology, image processing, optical signal prosessing and light
The various fields such as calculating all have the function that particularly important and huge potential application, therefore, find the new non-of excellent performance
Linear optical crystal becomes a hot spot in functional material research.
Ultraviolet, deep ultraviolet light source has extremely wide in deep ultraviolet light spectroscopy, microelectronics, micromechanics, informatics etc. etc.
Wealthy application prospect, it is to obtain ultraviolet, deep ultraviolet coherent source primary hand to carry out frequency conversion using nonlinear optical crystal
One of section.The nonlinear optical crystal that can be used for ultraviolet band at present is mainly borate serial crystal.Borate nonlinear light
Learn crystal has unique advantage in ultraviolet band application aspect：First, due to B in B-O keys, O atom electronegativity difference very
Greatly, the transmission of ultraviolet light is conducive to；Second, since the energy gap between the valence band and conduction band of borate crystal is larger, thus have
Very high light injury threshold；3rd, due to B atoms not only can three-fold coordination but also can four-coordination, alternative species is extremely wide
It is general.The structure type of boron oxygen groups is varied in borate crystal, but building stone most basic in these boron oxygen groups
There are two types, a kind of is the BO of plane triangle coordination3Group, another kind are the BO of tetrahedral coordination4Group, BO3And BO4
Again poly group such as B can be formed by sharing oxygen atom in a different manner3O6, B3O7, B3O8, B3O9, B4O10Group etc..Together
When, meet the material of ultraviolet deep ultraviolet band demand to find, it is also contemplated that the cation in crystal is limited in period of element
I A, II A main groups in table, are conducive to the transmission of ultraviolet light.Selection alkali and alkaline earth metal ions borate salt system is studied, can
The nonlinear optical material met the requirements with therefrom finding.It is a kind of alkali borate to study earliest nonlinear optical crystal
Salt-potassium pentaborate (KB5O8·H2O), from mid-term the 1970s, people are to potassium pentaborate crystal growth and its nonlinear optical
Learn effect and begun to research, which, by efficient matchings, can obtain 200nm as a kind of good ultraviolet frequency double material
Following continuously adjustable ultraviolet light.In the 1980s, China scientist is found that new ultra-violet is non-thread in borate salt system
Property optical crystal β-BaB2O4(BBO) and LiB3O5, thus triggered the exploration upsurge of borate nonlinear optical crystal.90 years
Generation, KBe2BO3F2(KBBF)、CsB3O5(CBO)、CsLiB6O10(CLBO)、La2CaB10O19(LCB)、K2Al2B2O7(KABO)、
RECa4O(BO3)3(RECOB) etc. a series of ultraviolet deep ultraviolet nonlinear optical crystals are found successively.Although it have been found that above-mentioned
A variety of borate crystals, but above crystal all comes with some shortcomings, therefore it is still one to find new nonlinear optical crystal
A very important work.
In recent years, in Development of Novel nonlinear optical crystal, the optical property and mechanical performance of crystal are not only focused on, and
And increasingly pay attention to the preparation characteristic of crystal, it is desirable to which new crystalline material is easily prepared, and it is high can to obtain cheap large scale
The nonlinear optical crystal of quality.Alkaline earth metal cation is introduced in boron oxygen frame to improve the guidance of the design philosophy of its performance
Under, for anion based on boron oxygen functional motif, its band gap is larger, and two-photon absorption probability is small；Laser damage threshold is higher；Profit
In the stronger nonlinear optical effect of acquisition；B-O keys are passed through beneficial to broadband light.Cation selective alkaline-earth metal ions, its
Ultra-violet (UV) band is without d0The transition of electronics, is conducive to UV transmission.
Problem to be solved by this invention is to provide that a kind of transmission region is wider, and nonlinear second-order optical susceptibility is larger, energy
Enough realize phase matched, easily preparation and preferably inorganic one water monohydroxy of deep ultraviolet, the five line borate non-linear optical crystal of stability
Body material and its preparation method and application.
The content of the invention
It is an object of the present invention in order to make up the blank spectral regions of all kinds of laser transmitting optical maser wavelengths, so as to provide
A kind of transparent five line borate Ca of a water monohydroxy2B5O9OH·H2O nonlinear optical crystals.
Five line borate of a water monohydroxy is prepared easily to operate using hydro-thermal method it is a further object of the present invention to provide one kind
(Ca2B5O9OH·H2O) the method for nonlinear optical crystal.
It is yet another object of the invention to provide five line borate (Ca of a water monohydroxy2B5O9OH·H2O) nonlinear optical crystal
Performance evaluation；
Another object of the present invention is to provide five line borate (Ca of a water monohydroxy2B5O9OH·H2O) device for non-linear optical
Purposes.
One water monohydroxy of a kind of compound, five line borate nonlinear optical crystal of the present invention, the molecular formula of the crystal
For Ca2B5O9OH·H2O, molecular weight 313.23 belong to monoclinic system, space group Cc, and cell parameter is a=10.780 (3)B=6.5110 (19)C=12.339 (4)β=115.057 (19) °.
The preparation method of one water monohydroxy, the five line borate nonlinear optical crystal, crystal is prepared using hydro-thermal method,
Concrete operations follow these steps to carry out：
A, by CaCl2、Ca(CH3COO)2·H2O、CaSO4、Ca(ClO4)2、CaCO3Or Ca (NO3)2Being added to volume is
In the polytetrafluoroethyllining lining of the autoclave of 23-125mL, H is added3BO3Or B2O3, deionized water 10-70mL is added,
It is sufficiently mixed uniformly, obtain mixed solution；
B, mineralizer lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide or second two will be added in the mixed solution of step a
Amine mixes, and the volume ratio of mineralizer and mixed solution is 1:5-40；
C, the polytetrafluoroethyllining lining lid equipped with mixed solution in step b is screwed, the high pressure for loading respective volume is anti-
Answer in kettle, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, 120- is warming up to the speed of 10-60 DEG C/h of temperature
210 DEG C, constant temperature 10-30 days, then rate of temperature fall or cooled to room temperature with 1-50 DEG C/h of temperature；
E, open autoclave, the solution containing crystal is filtered, parse and determine through X-ray single crystal diffractometer, to obtain the final product
To transparent five line borate Ca of a water monohydroxy2B5O9OH·H2O nonlinear optical crystals.
Ca in step a2+And BO3 3-Molar ratio be 1:2-8, Ca2+And B2O3Molar ratio be 1:1-4.
Solution is placed in clean free of contamination autoclave by step c.
One water monohydroxy of compound, the five line borate nonlinear optical crystal is preparing times frequency generator, up or down frequency
The purposes of rate converter or optical parametric oscillator.
Five line borate nonlinear optical crystal of water monohydroxy of the present invention, its ultraviolet cut-on side in below 190nm,
Nonlinear optical effect is about 2 times of KDP, and space group Cc, the preparation of this crystal is simple, and growth cycle is short, used starting
Material toxicity is low small to human body murder by poisoning.
Method used in the present invention is hydro-thermal method, i.e., after starting material is proportionally mixed, passes through in temperature range
The reaction kettle high temperature reaction under high pressure of sealing, a transparent water monohydroxy five is can obtain by the method for program cooling or constant temperature
Line borate nonlinear optical crystal.
Five line borate nonlinear optical crystal of water monohydroxy of the present invention, following chemical reaction is pressed using hydro-thermal method
Formula prepares crystal：
(1)2CaCl2+5H3BO3→Ca2B5O9OH·H2O+4Cl-+4H2O+4H+
(2)2Ca(CH3COO)2·H2O+5H3BO3→Ca2B5O9OH·H2O+4CH3COO-+4H2O+4H+
(3)2CaSO4+5H3BO3→Ca2B5O9OH·H2O+2SO4 2-+4H2O+4H+
(4)2Ca(ClO4)2+5H3BO3→Ca2B5O9OH·H2O+4ClO4 -+4H2O+4H+
(5)2Ca(NO3)2+5H3BO3→Ca2B5O9OH·H2O+4NO3 -+4H2O+4H+
(6)2CaCO3+5H3BO3 Ca2B5O9OH·H2O+2CO3 2-+4H2O+4H+
(7)2CaCl2+5/2B2O3+7/2H2O→Ca2B5O9OH·H2O+4Cl-+4H+
(8)2Ca(CH3COO)2+5/2B2O3+7/2H2O→Ca2B5O9OH·H2O+4CH3COO-+4H+
(9)2CaSO4+5/2B2O3+7/2H2O→Ca2B5O9OH·H2O+2SO4 2-+4H+
(10)2Ca(ClO4)2+5/2B2O3+7/2H2O→Ca2B5O9OH·H2O+4ClO4 -+4H+
(11)2Ca(NO3)2+5/2B2O3+7/2H2O→Ca2B5O9OH·H2O+4NO3 -+4H+
(12)2CaCO3+5/2B2O3+7/2H2O Ca2B5O9OH·H2O+2CO3 2-+4H+
Raw material is to use commercially available reagent in the present invention, and the crystal obtained by method of the present invention is transparent, has
Easy to operate, the speed of growth is fast, and growth cycle is short, the advantages such as cost is low.
Five line borate nonlinear optical crystal of water monohydroxy of the present invention is wrapped as device for non-linear optical is prepared
Include and make times frequency generator, up or down frequency converter and optical parametric oscillator.Use one water monohydroxy, five line borates are non-
The nonlinear device that linear optical crystal makes, which includes, will transmit through at least a branch of at least a branch of frequency difference of incident fundamental wave generation
In the coherent light of incident light.
One water monohydroxy, the five line borate nonlinear optical crystal is to optical manufacturing precision without particular/special requirement.
Brief description of the drawings
Fig. 1 is the X-ray diffracting spectrum of the present invention；
Fig. 2 is crystal pattern of the present invention；
Fig. 3 is the fundamental diagram for the device for non-linear optical that the present invention makes, and is laser including (1), (2) are
Convex lens, (3) are Ca2B5O9OH·H2O nonlinear optical crystals, (4) are Amici prism, and (5) are filter plate, and ω is refraction
The frequency of light is equal to 2 times of incident light frequency or incident light frequency.
Embodiment
Below in conjunction with drawings and examples, the present invention is described in detail：
Embodiment 1
With chemical equation 2CaCl2+5H3BO3→Ca2B5O9OH·H2O+4Cl-+4H2O+4H+Prepare crystal：
A, it is in molar ratio CaCl2:H3BO3=1:5, by CaCl2It is added to poly- the four of the autoclave that volume is 23mL
In vinyl fluoride liner, H is added3BO3, deionized water 12mL is added, it is sufficiently mixed uniformly, obtains mixed solution；
B, the LiOH solution 1mL that mineralising agent concentration is 2mol/L will be added in the mixed solution of step a to mix, mineralizer with
The volume ratio of mixed solution is 1:12；
C, the polytetrafluoroethyllining lining lid equipped with mixed solution in step b is screwed, loads the clean nothing of respective volume
In the autoclave of pollution, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, 180 DEG C is warming up to the speed of 20 DEG C/h of temperature,
Constant temperature 10 days, then be cooled to room temperature with the rate of temperature fall of 2 DEG C/h of temperature；
E, autoclave is opened, the solution containing crystal is repeatedly filtered, is determined i.e. through the parsing of X-ray single crystal diffractometer
Obtain relatively transparent five line borate Ca of a water monohydroxy2B5O9OH·H2O nonlinear optical crystals.
Embodiment 2
With chemical equation 2Ca (CH3COO)2·H2O+5H3BO3→Ca2B5O9OH·H2O+4CH3COO-+4H2O+4H+System
Standby crystal：
A, it is in molar ratio Ca (CH3COO)2·H2O:H3BO3=1:4, by Ca (CH3COO)2·H2O is added to volume
In the polytetrafluoroethyllining lining of the autoclave of 80mL, H is added3BO3, deionized water 40mL is added, it is sufficiently mixed
It is even, obtain mixed solution；
B, the NaOH solution 1.0mL that mineralising agent concentration is 2mol/L will be added in the mixed solution of step a to mix, mineralizer
Volume ratio with mixed solution is 1:40；
C, the polytetrafluoroethyllining lining lid equipped with mixed solution in step b is screwed, loads the clean nothing of respective volume
In the autoclave of pollution, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, 200 DEG C is warming up to the speed of 30 DEG C/h of temperature,
Constant temperature 15 days, cooled to room temperature；
E, autoclave is opened, the solution containing crystal is repeatedly filtered, is determined i.e. through the parsing of X-ray single crystal diffractometer
Obtain relatively transparent five line borate Ca of a water monohydroxy2B5O9OH·H2O nonlinear optical crystals.
Embodiment 3
With chemical equation 2CaSO4+5H3BO3→Ca2B5O9OH·H2O+2SO4 2-+4H2O+4H+Prepare crystal：
A, it is in molar ratio CaSO4:H3BO3=1:8, by CaSO4It is added to poly- the four of the autoclave that volume is 23mL
In vinyl fluoride liner, H is added3BO3, deionized water 10mL is added, it is sufficiently mixed uniformly, obtains mixed solution；
B, the KOH solution 0.5mL that mineralising agent concentration is 2mol/L will be added in the mixed solution of step a to mix, mineralizer
Volume ratio with mixed solution is 1:20；
C, the polytetrafluoroethyllining lining lid equipped with mixed solution in step b is screwed, loads the clean nothing of respective volume
In the autoclave of pollution, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, 210 DEG C is warming up to the speed of temperature 60 C/h,
Constant temperature 20 days, then room temperature is down to the rate of temperature fall of 30 DEG C/h of temperature；
E, open autoclave, the solution containing crystal is filtered, parse and determine through X-ray single crystal diffractometer, to obtain the final product
To transparent five line borate Ca of a water monohydroxy2B5O9OH·H2O nonlinear optical crystals.
Embodiment 4
With chemical equation 2Ca (ClO4)2+5H3BO3→Ca2B5O9OH·H2O+4ClO4 -+4H2O+4H+Prepare crystal：
A, it is in molar ratio Ca (ClO4)2:H3BO3=1:6, by Ca (ClO4)2It is added to the reaction under high pressure that volume is 125mL
In the polytetrafluoroethyllining lining of kettle, H is added3BO3, deionized water 70mL is added, it is sufficiently mixed uniformly, obtains mixing molten
Liquid；
B, mineralizer ethylenediamine 2mL will be added in the mixed solution of step a to mix, the volume ratio of mineralizer and mixed solution
For 1:35；
C, the polytetrafluoroethyllining lining lid equipped with mixed solution in step b is screwed, loads the clean nothing of respective volume
In the autoclave of pollution, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, 120 DEG C is warming up to the speed of 10 DEG C/h of temperature,
Constant temperature 30 days, then room temperature is down to the rate of temperature fall of 1 DEG C/h of temperature；
E, autoclave is opened, the solution containing crystal is filtered, determines to obtain through the parsing of X-ray single crystal diffractometer
To transparent five line borate Ca of a water monohydroxy2B5O9OH·H2O nonlinear optical crystals.
Embodiment 5
With chemical equation 2Ca (NO3)2+5H3BO3→Ca2B5O9OH·H2O+4NO3 -+4H2O+4H+Prepare crystal：
A, it is in molar ratio Ca (NO3)2:H3BO3=1:2, by Ca (NO3)2It is added to the autoclave that volume is 23mL
Polytetrafluoroethyllining lining in, add H3BO3, deionized water 10mL is added, it is sufficiently mixed uniformly, obtains mixed solution；
B, mineralizer ammonium hydroxide 2mL in the mixed solution of step a is mixed, the volume ratio of mineralizer and mixed solution is 1:5；
C, the polytetrafluoroethyllining lining lid equipped with mixed solution in step b is screwed, loads the clean nothing of respective volume
In the autoclave of pollution, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, 210 DEG C is warming up to the speed of temperature 60 C/h,
Constant temperature 25 days, then room temperature is down to the rate of temperature fall of 25 DEG C/h of temperature；
E, open autoclave, the solution containing crystal is filtered, parse and determine through X-ray single crystal diffractometer, to obtain the final product
To transparent five line borate Ca of a water monohydroxy2B5O9OH·H2O nonlinear optical crystals.
Embodiment 6
With chemical equation 2CaCO3+5H3BO3 Ca2B5O9OH·H2O+2CO3 2-+4H2O+4H+Prepare crystal：
A, it is in molar ratio CaCO3:H3BO3=1:3, by CaCO3It is added to poly- the four of the autoclave that volume is 23mL
In vinyl fluoride liner, H is added3BO3, deionized water 12mL is added, it is sufficiently mixed uniformly, obtains mixed solution；
B, mineralizer ammonium hydroxide 2mL will be added in the mixed solution of step a to mix, the volume ratio of mineralizer and mixed solution is
1:6；
C, the polytetrafluoroethyllining lining lid where mixed solution in step b is screwed, loads the clean nothing of respective volume
In the autoclave of pollution, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, 210 DEG C is warming up to the speed of 10 DEG C/h of temperature,
Constant temperature 10 days, then room temperature is down to the rate of temperature fall of temperature 50 C/h；
E, autoclave is opened, the solution containing crystal is filtered, determines to obtain through the parsing of X-ray single crystal diffractometer
To transparent five line borate Ca of a water monohydroxy2B5O9OH·H2O nonlinear optical crystals.
Embodiment 7
With chemical equation 2CaCl2+5/2B2O3+7/2H2O→Ca2B5O9OH·H2O+4Cl-+4H+Prepare crystal：
A, it is in molar ratio CaCl2:B2O3=1:2.5, by CaCl2It is added to the poly- of the autoclave that volume is 23mL
In tetrafluoroethene liner, B is added2O3, deionized water 12mL is added, it is sufficiently mixed uniformly, obtains mixed solution.
B, by the mixed solution in step a, the LiOH solution 1mL that concentration is 2mol/L, mineralizer and mixed solution are added
Volume ratio be 1:12；
C, the polytetrafluoroethyllining lining lid where mixed solution in step b is screwed, loads clean free of contamination high pressure
In reaction kettle, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, 180 is risen to the heating rate of 20 DEG C/h of temperature
DEG C, constant temperature 10 days, then be cooled to room temperature with the rate of temperature fall of 2 DEG C/h of temperature；
E, autoclave is opened, the solution containing crystal is repeatedly filtered, parses and determines through X-ray single crystal diffractometer,
It can obtain relatively transparent five line borate Ca of a water monohydroxy2B5O9OH·H2O nonlinear optical crystals.
Embodiment 8
With chemical equation 2Ca (CH3COO)2+5/2B2O3+7/2H2O→Ca2B5O9OH·H2O+4CH3COO-+4H+Prepare
Crystal：
A, it is in molar ratio Ca (CH3COO)2·H2O:B2O3=1:2, by Ca (CH3COO)2·H2O is added to volume
In the polytetrafluoroethyllining lining of the autoclave of 80mL, B is added2O3, deionized water 40mL is added, it is sufficiently mixed
It is even, obtain mixed solution.
B, by the mixed solution in step a, the NaOH solution 1.0mL that concentration is 2mol/L is added, mineralizer is molten with mixing
The volume ratio of liquid is 1:40；
C, the polytetrafluoroethyllining lining lid where mixed solution in step b is screwed, loads clean free of contamination high pressure
In reaction kettle, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, 200 is risen to the heating rate of 30 DEG C/h of temperature
DEG C, constant temperature 15 days, cooled to room temperature；
E, autoclave is opened, the solution containing crystal is repeatedly filtered, parses and determines through X-ray single crystal diffractometer,
It can obtain relatively transparent five line borate Ca of a water monohydroxy2B5O9OH·H2O nonlinear optical crystals.
Embodiment 9
With chemical equation 2CaSO4+5/2B2O3+7/2H2O→Ca2B5O9OH·H2O+2SO4 2-+4H+Prepare crystal：
A, it is in molar ratio CaSO4:B2O3=1:4, by CaSO4It is added to poly- the four of the autoclave that volume is 23mL
In vinyl fluoride liner, B is added2O3, deionized water 10mL is added, it is sufficiently mixed uniformly, obtains mixed solution.
B, by the mixed solution in step a, the KOH solution 0.5mL that concentration is 2mol/L, mineralizer and mixed solution are added
Volume ratio be 1:20；
C, the polytetrafluoroethyllining lining lid where mixed solution in step b is screwed, loads clean free of contamination high pressure
In reaction kettle, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, 210 is risen to the heating rate of temperature 60 C/h
DEG C, constant temperature 20 days, then be cooled to room temperature with the rate of temperature fall of 30 DEG C/h of temperature；
E, autoclave is opened, the solution containing crystal is filtered, parses and determines through X-ray single crystal diffractometer, you can
Obtain transparent five line borate Ca of a water monohydroxy2B5O9OH·H2O nonlinear optical crystals.
Embodiment 10
With chemical equation 2Ca (ClO4)2+5/2B2O3+7/2H2O→Ca2B5O9OH·H2O+4ClO4 -+4H+Prepare crystal：
A, it is in molar ratio Ca (ClO4)2:B2O3=1:3, by Ca (ClO4)2It is added to the reaction under high pressure that volume is 125mL
In the polytetrafluoroethyllining lining of kettle, B is added2O3, deionized water 70mL is added, it is sufficiently mixed uniformly, obtains mixing molten
Liquid.
B, mineralizer ethylenediamine 2mL will be added in the mixed solution in step a, the volume ratio of mineralizer and mixed solution is
1:35；
C, the polytetrafluoroethyllining lining lid where mixed solution in step b is screwed, loads clean free of contamination high pressure
In reaction kettle, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, 120 is risen to the heating rate of 10 DEG C/h of temperature
DEG C, constant temperature 30 days, then rate of temperature fall or cooled to room temperature with 1 DEG C/h of temperature；
E, autoclave is opened, the solution containing crystal is filtered, parses and determines through X-ray single crystal diffractometer, you can
Obtain transparent five line borate Ca of a water monohydroxy2B5O9OH·H2O nonlinear optical crystals.
Embodiment 11
With chemical equation 2Ca (NO3)2+5/2B2O3+7/2H2O→Ca2B5O9OH·H2O+4NO3 -+4H+Prepare crystal：
A, it is in molar ratio Ca (NO3)2:B2O3=1:1, by Ca (NO3)2It is added to the autoclave that volume is 23mL
In polytetrafluoroethyllining lining, B is added2O3, deionized water 10mL is added, it is sufficiently mixed uniformly, obtains mixed solution.
B, the mixed solution in step a is added into mineralising with regard to ammonium hydroxide 2mL, the volume ratio of mineralizer and mixed solution is 1:5；
C, the polytetrafluoroethyllining lining lid where mixed solution in step b is screwed, loads clean free of contamination high pressure
In reaction kettle, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, 210 is risen to the heating rate of temperature 60 C/h
DEG C, constant temperature 25 days, then be cooled to room temperature with the rate of temperature fall of 25 DEG C/h of temperature；
E, autoclave is opened, the solution containing crystal is filtered, parses and determines through X-ray single crystal diffractometer, you can
Obtain transparent five line borate Ca of a water monohydroxy2B5O9OH·H2O nonlinear optical crystals.
Embodiment 12
With chemical equation 2CaCO3+5/2B2O3+7/2H2O Ca2B5O9OH·H2O+2CO3 2-+4H+Prepare crystal：
A, it is in molar ratio CaCO3:B2O3=1:1.5, by CaCO3It is added to the poly- of the autoclave that volume is 23mL
In tetrafluoroethene liner, B is added2O3, deionized water 12mL is added, it is sufficiently mixed uniformly, obtains mixed solution；
B, mineralizer ammonium hydroxide 2mL will be added in the mixed solution of step a to mix, the volume ratio of mineralizer and mixed solution is
1:6；
C, the polytetrafluoroethyllining lining lid where mixed solution in step b is screwed, loads the clean nothing of respective volume
In the autoclave of pollution, reaction kettle piston is screwed；
D, the autoclave in step c is placed in insulating box, 210 DEG C is warming up to the speed of 10 DEG C/h of temperature,
Constant temperature 10 days, then room temperature is down to the rate of temperature fall of temperature 50 C/h；
E, autoclave is opened, the solution containing crystal is filtered, parses and determines through X-ray single crystal diffractometer, you can
Obtain transparent five line borate Ca of a water monohydroxy2B5O9OH·H2O nonlinear optical crystals.
Embodiment 13：
By in embodiment 1-12 gained five line borate nonlinear optical crystal of any one water monohydroxy, as shown in attached drawing 3
It is placed on 3 position, at room temperature, with tune Q Nd:Light source is made in the 1064nm outputs of YAG laser, it was observed that significantly
532nm frequency doubling green lights export, and output intensity is about 2 times of equal conditions KDP；
Fig. 3 is shown, by adjusting Q Nd:YAG laser 1 sends the infrared beam that wavelength is 1064nm and is penetrated through convex lens 2
Enter Ca2B5O9OH·H2O nonlinear optical crystals, generation wavelength are the green frequency doubled light of 532nm, and outgoing beam 4 is containing wavelength
The infrared light of 1064nm and the green light of 532nm, obtain the frequency doubled light that wavelength is 532nm after filtered 5 elimination.
Claims (3)
1. a kind of one water monohydroxy of compound, five line borate nonlinear optical crystal, it is characterised in that the molecular formula of the crystal is
Ca2B5O9OH·H2O, molecular weight 313.23 belong to monoclinic system, and space group isCc, cell parameter is a=10.780 (3)
, b=6.5110 (19), c=12.339 (4),β= 115.057(19)°。
2. the preparation method of five line borate nonlinear optical crystal of water monohydroxy according to claim 1, its spy are
Crystal is prepared using hydro-thermal method, concrete operations follow these steps to carry out：
A, by CaCl2、Ca(CH3COO)2·H2O、CaSO4、Ca(ClO4)2、CaCO3Or Ca (NO3)2It is 23-125 to be added to volume
In the polytetrafluoroethyllining lining of the autoclave of mL, H is added3BO3Or B2O3, deionized water 10-70 mL are added, fill it
Divide and be uniformly mixed, obtain mixed solution, wherein Ca2+And BO3 3-Molar ratio be 1:2-8, Ca2+And B2O3Molar ratio be 1:1-
4；
B, mineralizer lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide or ethylenediamine will be added in the mixed solution of step a to mix
Close, the volume ratio of mineralizer and mixed solution is 1:5-40；
C, the polytetrafluoroethyllining lining lid equipped with mixed solution in step b is screwed, loads the autoclave of respective volume
In, reaction kettle piston is screwed, wherein solution is placed in clean free of contamination autoclave；
D, the autoclave in step c is placed in insulating box, 120-210 is warming up to the speed of 10-60 DEG C/h of temperature
DEG C, constant temperature 10-30 days, then rate of temperature fall or cooled to room temperature with 1-50 DEG C/h of temperature；
E, autoclave is opened, the solution containing crystal is filtered, parses and determines through X-ray single crystal diffractometer, that is, obtain
Bright Ca2B5O9OH·H2O nonlinear optical crystals.
3. one water monohydroxy of compound, five line borate nonlinear optical crystal according to claim 1 is preparing frequency multiplication
The purposes of device, up or down frequency converter or optical parametric oscillator.
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| CN103114334A (en) * | 2011-11-17 | 2013-05-22 | 中国科学院新疆理化技术研究所 | Compound tetrahydroxy barium borate and tetrahydroxy barium borate nonlinear optical crystal as well as preparation method and application |
| CN103696006A (en) * | 2012-09-28 | 2014-04-02 | 中国科学院新疆理化技术研究所 | Monohydrate hydroxyl strontium borate and monohydrate hydroxyl strontium borate nonlinear optical crystal, and preparation method and application of monohydrate hydroxyl strontium borate nonlinear optical crystal |
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| CN103114334A (en) * | 2011-11-17 | 2013-05-22 | 中国科学院新疆理化技术研究所 | Compound tetrahydroxy barium borate and tetrahydroxy barium borate nonlinear optical crystal as well as preparation method and application |
| CN103696006A (en) * | 2012-09-28 | 2014-04-02 | 中国科学院新疆理化技术研究所 | Monohydrate hydroxyl strontium borate and monohydrate hydroxyl strontium borate nonlinear optical crystal, and preparation method and application of monohydrate hydroxyl strontium borate nonlinear optical crystal |
Non-Patent Citations (1)
| Title |
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| A new mixed metal borate of BaPb[B5O9(OH)]·H2O with acentric structure;Han-QingWu et al;《Inorganic Chemistry Communications》;20130925;第37卷;第77页右栏第1-21行 * |
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