CN108286071A - Nonlinear optical crystal alkali metal fluosilicate boron beryllium acid ammonium salt and its preparation method and application - Google Patents
Nonlinear optical crystal alkali metal fluosilicate boron beryllium acid ammonium salt and its preparation method and application Download PDFInfo
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- CN108286071A CN108286071A CN201710016158.1A CN201710016158A CN108286071A CN 108286071 A CN108286071 A CN 108286071A CN 201710016158 A CN201710016158 A CN 201710016158A CN 108286071 A CN108286071 A CN 108286071A
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
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- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
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Abstract
The present invention provides the nonlinear optical crystal alkali metal fluosilicate boron beryllium acid ammonium salt and its preparation method and application of a series of new, the chemical general formula (NH of the crystal4)xM1‑xBe2BO3F2, abbreviation AMBBF, wherein x are ranging from：0<x<1；The one kind of M in alkali metal K, Rb, Cs.The serial crystal does not have symmetrical centre, belongs to trigonal system, space group is R32.The crystal AMBBF of the present invention has excellent optical property, NH in crystal4 +Ion and F‑Between hydrogen bond can effective enhancement layer intermolecular forces, the layer growth habit of crystal has been effectively relieved；In addition, AKBBF, ARBBF, ACBBF shortens c-axis compared with ABBF, RBBF, CBBF respectively, it enhances the nonlinear effect of crystal, increase the birefringence of crystal, so that the crystal AMBBF of the present invention has both the advantages of ABBF and MBBF crystal, especially AKBBF is in aspect of performance almost as KBBF, and interlaminar action power is also improved.The crystal AMBBF of the present invention can meet from infrared the needs of being used to deep ultraviolet light area nonlinear optical crystal.
Description
Technical field
The present invention relates to a series of new optoelectronic functional materials and its growing methods and purposes, more particularly to a series of
Alkali metal fluosilicate boron beryllium acid ammonium salt non-linear optical crystal material and its preparation method and application.
Background technology
The nonlinear optical effect of crystal refers to logical by certain incident direction when a branch of laser with certain polarization direction
When crossing one block of nonlinear optical crystal (such as borate family nonlinear optical crystal), the frequency of the light beam will change.
Crystal with non-linear optical effect is known as nonlinear optical crystal.Laser is carried out using nonlinear optical crystal
Frequency conversion widens the range of optical maser wavelength, makes being more widely applied for laser.Especially borate family nonlinear optical crystal
Such as BaB2O4(BBO)、LiB3O5(LBO)、MBe2BO3F2(MBBF, M=K, Rb, Cs), Sr2Be2B2O7(SBBO)、Ba2Be2B2O7
(TBO)、K2Al2B2O7(KABO)、BaAl2B2O7(BABO) etc. crystal are received much attention with its excellent optical property.Optics shines
Phase, photoengraving, precision instrument processing and other fields have deep ultraviolet laser coherent source urgent demand, that is, need to have excellent performance
Deep ultraviolet nonlinear optical crystal.
The basic structure primitive of bbo crystal is (B3O6)3-Plane group, this group have big conjugatedπbond so that
The ultraviolet absorption edge of BBO limits application of the crystal in ultra-violet (UV) band in 189nm or so；And big conjugatedπbond also result in it is larger
Birefringence (Δ n=0.12), to limit it harmonic generation efficiency and harmonic wave light quality.
MBBF (M=K, Rb, Cs, difference abbreviation KBBF, RBBF, CBBF) belongs to isomorphism crystal, and basic structure primitive is
(BO3)3-Plane group, ultraviolet cut-on side is 147 respectively, 160,151nm, birefringence is 0.077 respectively, 0.073,
0.058.Wherein KBBF and RBBF has been shown to generate 177.3 and 193nm ultraviolet lights, because its all have it is moderate two-fold
Rate is penetrated, very wide phase matching ranges may be implemented, is current classic deep ultraviolet nonlinear optical crystal.But due to KBBF
It is a kind of crystal of layer structure with RBBF, leans on electrostatic attraction between layers rather than be connected by valence link, stratiform
Habit is serious, and in the directions z, the speed of growth is very slow, and the monocrystal lamination grown is apparent, and crystal is not easy long thickness.
The basic structure primitive of SBBO is also (BO3)3-Plane group, but it replaces fluorine ion with oxygen so that layer and layer it
Between be connected with each other by oxygen bridge, improve the stratiform habit of KBBF, and each layer of structure then keeps being basically unchanged.SBBO is not only
With larger macroscopical Clock Multiplier Factor, low ultraviolet absorption edge (165nm), moderate birefringence (Δ n=0.06), and also it is thorough
Bottom overcomes the stratiform habit of crystal, solves the problems, such as crystal growth.On this basis, (BO is kept3)3-The structure bar of group
Part is basically unchanged, and replaces kation S r2+With Be atoms, a series of non-linear optical crystals such as TBO, KABO, BABO are had developed in succession
Body, they are referred to as SBBO group crystals.Although they overcome the stratiform habit of KBBF crystal growths, these crystal are at present
Until can't replace KBBF monocrystalline because the structural intergrity of SBBO and TBO crystal is bad, the optics that macro property is shown
Uniformity is excessively poor, can not also be applied in practical devices at present；The structural intergrity of KABO and BABO crystal is fine, tool
There is preferable optical homogeneity, but since Al is instead of Be, their ABSORPTION EDGE red shift is arrived 180nm or so, is difficult to dark purple
Outer harmonic wave.
The basic structure primitive of LBO is by (B3O6)3-A B atom in group becomes four-coordination to shape by three-fold coordination
At (B3O7)5-Group.It has larger Clock Multiplier Factor, and ultraviolet absorption edge is in 160nm or so, but due in real crystal
(B3O7)5-Group interconnects, form the coiled strand at 45 ° with z-axis in space and can not be arranged in parallel in lattice, make
The birefringence of crystal drops too low (Δ n=0.04~0.05) so that it ultra-violet (UV) band phase matching ranges by
Serious limitation, the advantage for keeping band gap wide fail to give full play to.
We design the crystal NH of synthesis before making the present invention4Be2BO3F2(ABBF) there is more excellent optical property, wherein
NH4 +Ion and F-Between hydrogen bond can effective enhancement layer intermolecular forces, the layer growth habit of crystal has been effectively relieved, can expire
Enough from the infrared demand used to deep ultraviolet light area nonlinear optical crystal.However, relative to KBBF (Δ n=0.077), ABBF
C-axis it is elongated, so that its birefringence is reduced (Δ n=0.055), this is unfavorable, and unit cell to deep ultraviolet phase matched
In (BO3)3-Group number density becomes smaller, and nonlinear effect is caused also to reduce (d compared with KBBFeff=0.9348 × KBBF).Cause
This, on the basis of keeping above-mentioned this paracrystalline organizations of KBBF families, part mixes NH4 +While enhancement layer intermolecular forces,
The length for shortening c-axis as possible is conducive to enhance nonlinear effect, increases birefringence, to obtain the better deep ultraviolet of performance
Nonlinear optical crystal.
Invention content
It is an object of the invention to overcome the shortcomings of existing crystal, it is non-to provide a series of new alkali metal fluosilicate boron beryllium acid ammonium salts
Linear optical crystal.
Another object of the present invention is to provide the growth sides of the alkali metal fluosilicate boron beryllium acid ammonium salt nonlinear optical crystal
Method.
It is also an object of the present invention to provide the purposes of the alkali metal fluosilicate boron beryllium acid ammonium salt nonlinear optical crystal.
To achieve the purpose of the present invention, the present invention provides the following technical solutions：
The present invention provides the alkali metal fluosilicate boron beryllium acid ammonium salt crystal, and chemical general formula is (NH4)xM1-xBe2BO3F2, referred to as
AMBBF, wherein x are ranging from：0<x<1；The one kind of M in alkali metal K, Rb, Cs.
Alkali metal fluosilicate boron beryllium acid ammonium salt of the present invention is nonlinear optical crystal；The serial crystal does not all have symmetrical
Center belongs to trigonal system, space group R32.As illustrative example, (NH4)0.28K0.72Be2BO3F2Cell parameter
Forα=β=90 °, γ=120 °, z=3, unit-cell volume(NH4)0.83Rb0.17Be2BO3F2Cell parameter be
α=β=90 °, γ=120 °, z=3, unit-cell volume(NH4)0.97Cs0.03Be2BO3F2Cell parameter be α=β=90 °, γ=120 °, z=3, unit-cell volume
There is the nonlinear optical crystal of the present invention stronger phase matched ability (to be surveyed using powder frequency doubling test method
Amount, powder SHG effect is about 1.0 times of KH2PO4(KDP))；Its ultraviolet absorption edge is shorter than 160nm.In addition, the crystalline substance of the present invention
Body can realize Nd:2 frequencys multiplication of YAG (λ=1064nm), the harmonic oscillator of 3 frequencys multiplication, 4 frequencys multiplication, 5 frequencys multiplication, even 6 frequencys multiplication, very
To for generating the harmonic wave light output more shorter than 200nm.Further more, the crystal of the present invention is mono-crystalline structures, water white transparency, in air
In do not deliquesce, chemical stability is good (being heated to about 450-600 DEG C just to decompose).Wherein, AKBBF has closer compared with ABBF
The excellent properties of KBBF, especially closer to KBBF in terms of birefringence and nonlinear effect.ARBBF and ACBBF also respectively compared with
RBBF and CBBF is improved in terms of birefringence and nonlinear effect.
The present invention provides the growing method of the alkali metal fluosilicate boron beryllium acid ammonium salt nonlinear optical crystal.With MBe2BO3F2
(abbreviation MBBF), NH4Be2BO3F2(abbreviation ABBF) is raw material, with H3BO3-NH4F-MF is mineralizer system, passes through hydro-thermal legal system
The standby crystal；
Wherein, the one kind of the M in MBBF, MF in alkali metal K, Rb, Cs.
According to the present invention, the molar ratio (MBBF+ABBF) of each raw material and mineralizer in hydro-thermal method：H3BO3：(NH4F+MF) it is
(0.5~3)：(0.5~2.5)：(2.0~5.0)；Wherein, the molar ratio of MBBF and ABBF is (0.2~3.5)：1；NH4F and MF
Molar ratio be (1.5~6.0)：1.
According to the present invention, the raw material MBBF and ABBF and mineralizer NH is adjusted4The molar ratio of F and MF can obtain different alkali
Metal and NH4 +The alkali metal fluosilicate boron beryllium acid ammonium salt crystal of proportioning.
Preferably, H3BO3Molar concentration is 0.5~1.5mol/L.
Preferably, NH4F molar concentrations are 2.0~3.5mol/L.
According to the present invention, the operating procedure of the hydro-thermal method is as follows：MBBF compounds, ABBF compounds and mineralizer are put
Enter in water heating kettle, water is added, it is 290~330 DEG C to be warming up to top crystallization temperature, and temperature of lower is 330~360 DEG C, constant temperature 30
After~45 days, 50 DEG C are cooled to 5 DEG C/h, stops heating, after sample cooling, cleaned, you can obtain of the present invention one
Serial alkali metal fluosilicate boron beryllium acid ammonium salt nonlinear optical crystal.
Preferably, MBBF compounds, ABBF compounds need to after mixing be placed into mineralizer in the operating procedure
In water heating kettle.
Preferably, in the operating procedure water addition be water heating kettle volume 50%~85%, preferably 55%~
70%.
Wherein it is preferred to which sample carries out cleaning processing after being cooled to 20~30 DEG C.
Wherein, it is or mixtures thereof water, organic solvent to clean the solvent used, and above-mentioned multi-solvents may be used several times
It is cleaned.Organic solvent is not particularly limited, the solvent that need to only use is the solvent inert to crystal.As example
Property example, organic solvent can be selected from nitrile solvents (such as acetonitrile), aromatic hydrocarbon solvent (such as benzene, toluene), alcohols solvent (such as first
Alcohol, ethyl alcohol, isopropanol, normal propyl alcohol), ether solvent (such as ether), esters solvent (such as ethyl acetate), halogenated hydrocarbon solvent (such as
Dichloromethane, carbon tetrachloride) in one or more, preferably ethyl alcohol.
Wherein, the crystalline size that the preparation method obtains is more than 3.0mm.
Wherein, the crystal that the preparation method obtains can alleviate stratiform habit, shorten the length of crystal c axis, favorably
In the nonlinear effect of enhancing crystal, increase the birefringence of crystal.As illustrative example, (NH4)0.83Rb0.17Be2BO3F2The c-axis length of crystal isC-axis compared with RBBFIt is shortWhat is calculated has
Imitate nonlinear effect coefficient deff=1.0013 × RBBF, birefringence 0.074；(NH4)0.97Cs0.03Be2BO3F2The c of crystal
Shaft length isC-axis compared with CBBFIt is shortThe effective nonlinear effect coefficient d calculatedeff=
1.0291 × CBBF, birefringence 0.064.
Further more, there are ammonium ion, alkali metal ion and fluorine ions in the crystal that the preparation method is prepared, wherein
NH4 +It is total to occupy-place with alkali metal ion, it, can relief layer by the effect of hydrogen bond since ammonium ion and fluorine ion can generate hydrogen bond
Shape habit；Wherein, NH4 +It is total to occupy-place with K ions so that AKBBF is compared with ABBF in aspect of performance closer to KBBF.Relative to
For ABBF, interlamellar spacing is not only shortened, also increases birefringence.Specifically, (the NH being prepared4)0.28K0.72Be2BO3F2The c-axis length of crystal isC-axis compared with KBBFOnly growCompared with ABBF
C-axis It is shortThe effective nonlinear effect coefficient d calculatedeff=0.9935 × KBBF, birefringence
0.075, compared with ABBF (deff=0.9348 × KBBF, birefringence 0.055) it is more leaned in terms of nonlinear effect and birefringence
Nearly KBBF.
The present invention provides the purposes of the alkali metal fluosilicate boron beryllium acid ammonium salt nonlinear optical crystal, which is used for laser
The frequency transformation of laser output.
The present invention provides the purposes of the alkali metal fluosilicate boron beryllium acid ammonium salt nonlinear optical crystal, which is used for wavelength
2 frequencys multiplication or 3 frequencys multiplication or 4 frequencys multiplication or 5 frequencys multiplication even the harmonic wave light output of 6 frequencys multiplication are generated for the laser beam of 1064nm.
The present invention provides the purposes of the alkali metal fluosilicate boron beryllium acid ammonium salt nonlinear optical crystal, and the crystal is low for generating
In the harmonic wave light output of 200nm.
The present invention provides the purposes of the alkali metal fluosilicate boron beryllium acid ammonium salt nonlinear optical crystal, which is used for deep ultraviolet
The harmonic oscillator in area, optical parameter and amplifying device and fiber waveguide device.
The present invention provides the purposes of the alkali metal fluosilicate boron beryllium acid ammonium salt nonlinear optical crystal, which is used for from infrared
To the optical parameter and amplifying device of dark purple outskirt.
Beneficial effects of the present invention：
The crystal AMBBF of the present invention has excellent optical property, NH in crystal4 +Ion and F-Between hydrogen bond can have
Enhancement layer intermolecular forces are imitated, the layer growth habit of crystal has been effectively relieved；In addition, AKBBF, ARBBF, ACBBF respectively compared with
ABBF, RBBF, CBBF shorten c-axis, enhance the nonlinear effect of crystal, increase the birefringence of crystal, so that
The crystal AMBBF of the present invention has both the advantages of ABBF and MBBF crystal, especially AKBBF aspect of performance almost with KBBF mono-
Sample, and interlaminar action power is also improved.The crystal AMBBF of the present invention can meet from infrared to deep ultraviolet light area nonlinear optical
Learn the demand that crystal uses.
Description of the drawings
Fig. 1 is typical case signal of the alkali metal fluosilicate boron beryllium acid ammonium salt crystal as frequency-doubling crystal application non-linear hour optical effect
Figure, wherein 1 is laser, 2 be incoming laser beam, and 3 be the alkali metal fluosilicate boron beryllium acid ammonium salt through crystal post-processing and optical manufacturing
Monocrystalline, 4 be generated shoot laser beam, and 5 be filter plate.
Fig. 2 is alkali metal fluosilicate boron beryllium acid ammonium salt crystal structure schematic diagram.
Fig. 3 is 1 (NH of embodiment4)0.28K0.72Be2BO3F2Monocrystalline is pulverized last X ray diffracting spectrum.
Fig. 4 is 2 (NH of embodiment4)0.83Rb0.17Be2BO3F2Monocrystalline is pulverized last X ray diffracting spectrum.
Fig. 5 is 3 (NH of embodiment4)0.97Cs0.03Be2BO3F2Monocrystalline is pulverized last X ray diffracting spectrum.
Fig. 6 is 1 (NH of embodiment4)0.28K0.72Be2BO3F2EDS (Electronic Dispersive after monocrystalline cleaning
Spectrometer) energy spectrum diagram.
Fig. 7 is 2 (NH of embodiment4)0.83Rb0.17Be2BO3F2EDS (Electronic after monocrystalline cleaning
Dispersive Spectrometer) energy spectrum diagram.
Fig. 8 is 3 (NH of embodiment4)0.97Cs0.03Be2BO3F2EDS (Electronic after monocrystalline cleaning
Dispersive Spectrometer) energy spectrum diagram.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read recorded content of the invention, this field skill
Art personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within limited range of the present invention.
Unless otherwise indicated, the raw materials and reagents used in embodiment are commercial goods.
Embodiment 1
Using Hydrothermal Growth (NH4)0.28K0.72Be2BO3F2Monocrystalline
Crystal growing apparatus is Resistant heating stove, and temperature controlling instruments is that 908PHK20 types may be programmed automatic temperature control instrument.
Raw materials used and mineralizer：
Concrete operation step is as follows：Select H3BO3-NH4F-KF mineralizer systems, by above-mentioned raw materials and mine in control box
After agent is weighed up by above-mentioned dosage, it is fitted into the water heating kettle that capacity is 1600ml, then pour into 900ml distilled water, reaction kettle is put
Enter in the Resistant heating stove and is to slowly warm up to 300 DEG C/350 DEG C (upper temps/temperature of lower), constant temperature 30 days.Again with
5 DEG C of rate is cooled to 50 DEG C per hour, closes stove, is cleaned with water and alcohol after sample cooling, that is, it is 4.0 to obtain size
(the NH of × 4.0 × 3.5mm or so4)0.28K0.72Be2BO3F2Crystal.X-ray analysis, gained will be carried out after crystal grind into powder
Collection of illustrative plates such as Fig. 3.(NH4)0.28K0.72Be2BO3F2Cell parameter beα
=β=90 °, γ=120 °, z=3, unit-cell volumeFor ABBF, interlamellar spacing is not only shortened,
Also increase birefringence.C-axis of its c-axis compared with KBBFOnly growC-axis compared with ABBF
It is shortThe effective nonlinear effect coefficient d calculatedeff=0.9935 × KBBF, birefringence 0.075, compared with ABBF (deff
=0.9348 × KBBF, birefringence 0.055) in the aspect of performance such as nonlinear effect and birefringence closer to KBBF.
Embodiment 2
Using Hydrothermal Growth (NH4)0.83Rb0.17Be2BO3F2Monocrystalline
Crystal growing apparatus is Resistant heating stove, and temperature controlling instruments is that 908PHK20 types may be programmed automatic temperature control instrument.
Raw materials used and mineralizer：
Concrete operation step is as follows：Select H3BO3-NH4F-RbF mineralizer systems, by above-mentioned raw materials and mine in control box
After agent is weighed up by above-mentioned dosage, it is fitted into the water heating kettle that capacity is 1600ml, then pour into 900ml distilled water, reaction kettle is put
Enter in the Resistant heating stove and is to slowly warm up to 300 DEG C/350 DEG C (upper temps/temperature of lower), constant temperature 30 days.Again with
5 DEG C of rate is cooled to 50 DEG C per hour, closes stove, is cleaned with water and alcohol after sample cooling, that is, it is 3.8 to obtain size
(the NH of × 3.8 × 3.0mm or so4)0.83Rb0.17Be2BO3F2Crystal.X-ray analysis, institute will be carried out after crystal grind into powder
Obtain collection of illustrative plates such as Fig. 4.(NH4)0.83Rb0.17Be2BO3F2Cell parameter be
α=β=90 °, γ=120 °, z=3, unit-cell volumeIts c-axis of c-axis length compared with RBBF
It is shortThe effective nonlinear effect coefficient d calculatedeff=1.0013 × RBBF, birefringence 0.074.Embodiment 3
Using Hydrothermal Growth (NH4)0.97Cs0.03Be2BO3F2Monocrystalline
Crystal growing apparatus is Resistant heating stove, and temperature controlling instruments is that 908PHK20 types may be programmed automatic temperature control instrument.
Raw materials used and mineralizer：
Concrete operation step is as follows：Select H3BO3-NH4F-CsF mineralizer systems, by above-mentioned raw materials and mine in control box
After agent is weighed up by above-mentioned dosage, it is fitted into the water heating kettle that capacity is 1600ml, then pour into 900ml distilled water, reaction kettle is put
Enter in the Resistant heating stove and is to slowly warm up to 310 DEG C/350 DEG C (upper temps/temperature of lower), constant temperature 30 days.Again with
5 DEG C of rate is cooled to 50 DEG C per hour, closes stove, is cleaned with water and alcohol after sample cooling, that is, it is 3.5 to obtain size
(the NH of × 3.5 × 3.0mm or so4)0.82K0.18Be2BO3F2Optical crystal.X-ray analysis will be carried out after crystal grind into powder,
Gained collection of illustrative plates such as Fig. 5.(NH4)0.97Cs0.03Be2BO3F2Cell parameter be
α=β=90 °, γ=120 °, z=3, unit-cell volumeC-axis of its c-axis compared with CBBF It is shortThe effective nonlinear effect coefficient d calculatedeff=1.0291 × CBBF, birefringence 0.064.Embodiment 4
The crystal that embodiment 1,2,3 obtains is processed to the laser 1 being placed in Fig. 1 shown devices and filter plate 5
Between (i.e. the position of reference numeral 3), at room temperature, with adjust Q Nd:YAG laser does input light source, incident wavelength 1064nm,
Observe apparent 532nm frequency doubling green lights output, output intensity is about 1.0 times of equal conditions KDP.
Embodiment 5
The crystal that embodiment 1,2,3 obtains is processed to the laser 1 being placed in Fig. 1 shown devices and filter plate 5
Between (i.e. the position of reference numeral 3), at room temperature, with adjust Q Nd:The frequency doubled light of YAG laser does input light source, incident wavelength
For 532nm, the ultraviolet light output of 266nm frequencys multiplication is observed.
Embodiment 6
The crystal that embodiment 1,2 obtains is processed the laser 1 that is placed in Fig. 1 shown devices and filter plate 5 it
Between (i.e. the position of reference numeral 3), at room temperature, with adjust Q Nd:The frequency tripling frequency doubled light of YAG laser does input light source, incident
Wavelength is 355nm, observable 177.3nm frequencys multiplication deep ultraviolet light output.
By the NaCaBe2B2O6 ammonium potassium obtained in embodiment 1-3, NaCaBe2B2O6 ammonium rubidium and NaCaBe2B2O6 ammonium caesium crystal clean into
Row EDS energy spectrum analysis, as a result respectively such as Fig. 6, Fig. 7 and Fig. 8.The peak of apparent F, O, N and K element as seen from Figure 6, it was demonstrated that fluorine
The presence of boron beryllium acid ammonium potassium crystal with f and f, O, N and K element.The peak of apparent F, O, N and Rb element as seen from Figure 7, it was demonstrated that fluorine
The presence of boron beryllium acid ammonium potassium crystal with f and f, O, N and Rb element.The peak of apparent F, O, N and Cs element as seen from Figure 8, it was demonstrated that fluorine
The presence of boron beryllium acid ammonium potassium crystal with f and f, O, N and Cs element.
The crystal obtained in embodiment 1-3 is subjected to elemental analysis and plasma emission spectrometry, respectively to crystal
In N element and alkali metal element carry out quantitative analysis, the comparison such as table 1 of experiment value and theoretical value (weight percent).
Table 1
More than, embodiments of the present invention are illustrated.But the present invention is not limited to the above embodiments.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. alkali metal fluosilicate boron beryllium acid ammonium salt crystal, it is characterised in that：The chemical general formula of the crystal is (NH4)xM1-xBe2BO3F2,
Wherein x is ranging from：0<x<1；The one kind of M in alkali metal K, Rb, Cs.
2. alkali metal fluosilicate boron beryllium acid ammonium salt crystal as described in claim 1, it is characterised in that：The alkali metal NaCaBe2B2O6 ammonium
Salt is nonlinear optical crystal.
Preferably, the crystal does not all have symmetrical centre, belongs to trigonal system, space group R32.
Preferably, the chemical formula of the crystal is (NH4)0.28K0.72Be2BO3F2, cell parameter is α=β=90 °, γ=120 °, z=3, unit-cell volume Alternatively, the chemical formula of the crystal is (NH4)0.83Rb0.17Be2BO3F2, cell parameter is α=β=90 °, γ=120 °, z=3, unit-cell volumeAlternatively, institute
The chemical formula for stating crystal is (NH4)0.97Cs0.03Be2BO3F2, cell parameter is α=β=90 °, γ=120 °, z=3, unit-cell volume
3. alkali metal fluosilicate boron beryllium acid ammonium salt crystal as claimed in claim 1 or 2, it is characterised in that：It is tested using powder frequency doubling
Method measures, and the powder SHG effect of the crystal is about 1.0 times of KH2PO4(KDP)；Its ultraviolet absorption edge is shorter than 160nm.
Preferably, the crystal is mono-crystalline structures, and water white transparency does not deliquesce in air, is heated to about 450-600 DEG C and just occurs
It decomposes.
4. a kind of growing method of alkali metal fluosilicate boron beryllium acid ammonium salt crystal as described in any one of claims 1-3, feature exist
In：With MBe2BO3F2(abbreviation MBBF), NH4Be2BO3F2(abbreviation ABBF) is raw material, with H3BO3-NH4F-MF is mineralizer body
System, the crystal is prepared by hydro-thermal method；Wherein, the one kind of the M in MBBF, MF in alkali metal K, Rb, Cs.
5. a kind of growing method of alkali metal fluosilicate boron beryllium acid ammonium salt crystal as claimed in claim 4, it is characterised in that：Hydro-thermal method
In each raw material and mineralizer molar ratio (MBBF+ABBF)：H3BO3：(NH4F+MF) it is (0.5~3)：(0.5~2.5)：(2.0
~5.0).
Preferably, the molar ratio of MBBF and ABBF is (0.2~3.5)：1；NH4The molar ratio of F and MF is (1.5~6.0)：1；
Preferably, H3BO3Molar concentration is 0.5~1.5mol/L；NH4F molar concentrations are 2.0~3.5mol/L.
6. a kind of growing method of alkali metal fluosilicate boron beryllium acid ammonium salt crystal as described in claim 4 or 5, it is characterised in that：Institute
The operating procedure for stating hydro-thermal method is as follows：MBBF compounds, ABBF compounds and mineralizer are put into water heating kettle, water is added, is risen
Temperature to top crystallization temperature is 290~330 DEG C, and temperature of lower is 330~360 DEG C, and constant temperature is cooled down after 30~45 days with 5 DEG C/h
To 50 DEG C, stop heating, after sample cooling, cleans, you can obtain the alkali metal fluosilicate boron beryllium acid ammonium salt crystal.
Preferably, MBBF compounds, ABBF compounds need to place into hydro-thermal after mixing with mineralizer in the operating procedure
In kettle.
Preferably, the addition of water is the 50%~85% of water heating kettle volume in the operating procedure；Preferably 55%~70%.
Preferably, sample carries out cleaning processing after being cooled to 20~30 DEG C in the operating procedure.
Preferably, it is or mixtures thereof water, organic solvent that the solvent used is cleaned in the operating procedure, be may be used above-mentioned more
Kind of solvent is performed in multiple times clean, organic solvent is not particularly limited, the solvent that need to only use is inert to crystal
Solvent.It is further preferred that organic solvent can be selected from nitrile solvents such as acetonitrile, aromatic hydrocarbon solvent such as benzene, toluene, alcohols solvent such as first
Alcohol, ethyl alcohol, isopropanol, normal propyl alcohol, ether solvent such as ether, esters solvent such as ethyl acetate, halogenated hydrocarbon solvent such as dichloromethane
It is one or more in alkane, carbon tetrachloride, preferably ethyl alcohol.
7. a kind of growing method of the alkali metal fluosilicate boron beryllium acid ammonium salt crystal as described in claim any one of 4-6, it is characterised in that：
The crystalline size that the preparation method obtains is more than 3.0mm.
8. the purposes of claim 1-3 any one of them alkali metal fluosilicate boron beryllium acid ammonium salt crystal, which swashs for laser
The frequency transformation of light output.
9. the purposes of claim 1-3 any one of them alkali metal fluosilicate boron beryllium acid ammonium salt crystal, the crystal for being to wavelength
1.064 μm of laser beam generates 2 frequencys multiplication or 3 frequencys multiplication or 4 frequencys multiplication or 5 frequencys multiplication even the harmonic wave light output of 6 frequencys multiplication.
Alternatively, the crystal is used to generate the harmonic wave light output less than 200nm.
10. the purposes of claim 1-3 any one of them alkali metal fluosilicate boron beryllium acid ammonium salt crystal, the non-linear optical crystal
Body is used for the harmonic oscillator of dark purple outskirt, optical parameter and amplifying device and fiber waveguide device；
Alternatively, optical parameter and amplifying device of the crystal for the outskirt from infrared to dark purple.
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| CN112575374A (en) * | 2019-09-30 | 2021-03-30 | 天津理工大学 | Compound cesium chlorofluorocarbonboron zincate and cesium chlorofluorocarbonboron zincate nonlinear optical crystal as well as preparation method and application thereof |
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| CN101050543A (en) * | 2006-04-07 | 2007-10-10 | 中国科学院理化技术研究所 | Method for growing rubidium fluoroboroberyllate/cesium monocrystal by hydrothermal method |
| CN105624785A (en) * | 2015-09-29 | 2016-06-01 | 中国科学院福建物质结构研究所 | Ammonium beryllium borate fluoride as nonlinear optical crystal as well as preparation method and application thereof |
| CN105624780A (en) * | 2015-09-29 | 2016-06-01 | 中国科学院福建物质结构研究所 | Nonlinear beryllium borate fluoride (BBF) optical crystal as well as preparation method and application thereof |
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| CN105624785A (en) * | 2015-09-29 | 2016-06-01 | 中国科学院福建物质结构研究所 | Ammonium beryllium borate fluoride as nonlinear optical crystal as well as preparation method and application thereof |
| CN105624780A (en) * | 2015-09-29 | 2016-06-01 | 中国科学院福建物质结构研究所 | Nonlinear beryllium borate fluoride (BBF) optical crystal as well as preparation method and application thereof |
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| CN112575374A (en) * | 2019-09-30 | 2021-03-30 | 天津理工大学 | Compound cesium chlorofluorocarbonboron zincate and cesium chlorofluorocarbonboron zincate nonlinear optical crystal as well as preparation method and application thereof |
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