CN108221053A - The preparation of novel nonlinear optical crystal and purposes - Google Patents
The preparation of novel nonlinear optical crystal and purposes Download PDFInfo
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- CN108221053A CN108221053A CN201810127256.7A CN201810127256A CN108221053A CN 108221053 A CN108221053 A CN 108221053A CN 201810127256 A CN201810127256 A CN 201810127256A CN 108221053 A CN108221053 A CN 108221053A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- 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
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- 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
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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Abstract
This application discloses a kind of inorganic compounds, which is characterized in that the chemical formula of the inorganic compound is：M2Ge(IO3)6Wherein, M is Li and/or Na；The inorganic compound belongs to hexagonal crystal system, space group P63, cell parameter isα=β=90 °, γ=120 °, Z=1.The inorganic compound shows strong frequency-doubled effect, and powder SHG coefficients are more than KH2PO4(KDP) 15 times, 32 times are reached as high as；Its powder SHG coefficients are measured under 2.05 μm of laser irradiations as KTiOPO4(KTP) 2 or 0.8 times of crystal, and can realize phase matched, it is the nonlinear optical material with potential using value.
Description
Technical field
This application involves inorganic compound, it is prepared and application as nonlinear optical crystal, belongs to inorganic material and leads
Domain.
Background technology
Nonlinear optical crystal is a kind of functional material for being widely used in field of photoelectric technology, can realize laser frequency
Holographic storage of conversion, the modulation of laser intensity and phase and laser signal etc..
The nonlinear optical crystal of current practice includes LiB3O5(LBO),β-BaB2O4(BBO),KH2PO4(KDP),
KTiOPO4(KTP), α-LiIO3Deng.With the development of laser technology and the appearance of tunable laser, device for non-linear optical hair
Exhibition is rapid, laser freuqency doubling, mixing, parametric oscillation and amplification；Electro-optical Modulation, deflection, Q-switch and optical dioptric device etc. go out in succession
It is existing.The above research and application, propose nonlinear optical material the requirement of more higher physics, chemical property,
Also promote the rapid development of nonlinear optical material.Second-order non-linear optical crystal material must have non-centrosymmetrical knot
Structure.
Invention content
According to the one side of the application, a kind of novel inorganic compound is provided, which shows strong times
Frequency effect, powder SHG coefficients are more than KH2PO4(KDP) 15 times, 32 times are reached as high as；It is measured under 2.05 μm of laser irradiations
Its powder SHG coefficients are KTiOPO4(KTP) 2 or 0.8 times of crystal, and can realize phase matched, it is with potential using value
Nonlinear optical material.
The inorganic compound, which is characterized in that the chemical formula of the inorganic compound is：
M2Ge(IO3)6
Wherein, M is Li and/or Na；
The inorganic compound belongs to hexagonal crystal system, space group P63, cell parameter is α=β=90 °, γ=120 °, Z=1.
The UV cut-off wavelength of the inorganic compound is 250~350nm.
As a kind of embodiment, work as M=Li, Li2Ge(IO3)6There is high transmittance in 310~2500nm spectral regions,
UV cut-off wavelength (about 321nm) between 315~325nm.
As a kind of embodiment, work as M=Na, Na2Ge(IO3)6Crystal there is wider transmission range, 250~
2500nm spectral regions have very high transmitance, UV cut-off wavelength (about 267nm) between 260~275.
In crystal structure in the inorganic compound, contain in each asymmetric cell there are one M, a Ge, an I and
Three O atoms.Each Ge atoms and 6 O atoms connect into GeO6Octahedron, and each I atoms connect to be formed with 3 O atoms
IO3Pyrometric cone, 6 IO3Pyrometric cone is connected to GeO by monodentate ligand6Octahedron forms the [Ge (IO of 0 dimension3)6]2-Anion base
Group.M atoms are filled in [Ge (IO3)6]2-In gap between anionic group；IO3 -Middle lone pair electrons are arranged along c-axis direction
Basically identical, this arrangement mode is conducive to increase the polarity of compound, so as to enhance its nonlinear optical coefficients.
As a kind of embodiment, M is Li in the chemical formula of the inorganic compound, and cell parameter isα=β=90 °, γ=120 °, Z=1.
Li2Ge(IO3)6Crystal structure it is as shown in Figure 1.Fig. 1 is perspective view of the crystal structure along c-axis direction.Each
Li, a Ge there are one containing in asymmetric cell, I and three O atom.Each Ge atoms and 6 O atoms connect into GeO6
Octahedron, and each I atoms connect to form IO with 3 O atoms3Pyrometric cone, 6 IO3Pyrometric cone is connected to by monodentate ligand
GeO6Octahedron forms the [Ge (IO of 0 dimension3)6]2-Anionic group.Li atoms are filled in [Ge (IO3)6]2-Between anionic group
Gap in.From figure 1 it appears that IO3 -Being arranged along c-axis direction for middle lone pair electrons is basically identical.This arrangement mode has
Conducive to the polarity of increase compound, so as to enhance its nonlinear optical coefficients.
As a kind of embodiment, M is Na in the chemical formula of the inorganic compound, and cell parameter isα=β=90 °, γ=120 °, Z=1.
Na2Ge(IO3)6Crystal structure it is as shown in Figure 2.Fig. 2 is perspective view of the crystal structure along c-axis direction.Each
Na, a Ge there are one containing in asymmetric cell, I and three O atom.Each Ge atoms and 6 O atoms connect into GeO6
Octahedron, and each I atoms connect to form IO with 3 O atoms3Pyrometric cone, 6 IO3Pyrometric cone is connected to by monodentate ligand
GeO6Octahedron forms the [Ge (IO of 0 dimension3)6]2-Anionic group.Na atoms are filled in [Ge (IO3)6]2-Between anionic group
Gap in.From figure 2 it can be seen that IO3 -Being arranged along c-axis direction for middle lone pair electrons is basically identical.This arrangement mode has
Conducive to the polarity of increase compound, so as to enhance its nonlinear optical coefficients.
According to the another aspect of the application, the preparation method of the inorganic compound is provided, which is characterized in that using hydro-thermal
It is prepared by method, by the raw mixture containing M element, Germanium, iodine and water, the crystallization under 180 DEG C~260 DEG C crystallization temperatures
It obtains；
In the raw mixture, the molal quantity of M element, the molal quantity of Germanium, the molal quantity of iodine and water volume
Ratio is：
M：Ge：I：Water=1~10mol：1mol：1~20mol：1~50L.
Preferably, in the raw mixture, the molal quantity of M element, the molal quantity of Germanium, iodine molal quantity with
Water volume ratio is：
M：Ge：I：Water=5mol：1mol：2~10mol：1~5L.
Preferably, the crystallization temperature is 180 DEG C~250 DEG C, and crystallization time is no less than 24 hours.
It is further preferred that the crystallization time is 24~260 hours.
Preferably, after the crystallization, after cooling the temperature to room temperature with 0.5~13 DEG C/h of rate of temperature fall, separation
Obtained solid is washed to get the inorganic compound.
Optionally, in the raw mixture, M element comes from lithium-containing compound and/or compounds containing sodium.
Preferably, the lithium-containing compound is selected from lithium nitrate, lithium chloride, lithium fluoride, lithia, lithium carbonate, biphosphate
At least one of lithium.It is further preferred that the lithium salts is lithium carbonate.
Preferably, the compounds containing sodium is selected from sodium nitrate, sodium chloride, sodium fluoride, sodium oxide molybdena, sodium carbonate, biphosphate
At least one of sodium.It is further preferred that the lithium salts is sodium carbonate.
Preferably, in the raw mixture, Germanium is from least one of nitric acid germanium, germanium chloride, germanium oxide.Into
Preferably, the Germanium comes from germanium oxide to one step.
Preferably, in the raw mixture, iodine is from least one of iodic anhydride, acid iodide, periodic acid.
It is further preferred that the iodine comes from I2O5。
According to the another aspect of the application, application of the inorganic compound as non-linear optical crystal material is provided.
The non-linear optical crystal material, which is characterized in that containing any of the above-described inorganic compound crystal and/or according to any of the above-described
The inorganic compound crystal that method is prepared.
As M=Li, Li2Ge(IO3)6Crystal exports very strong 532nm green lights, powder under 1064nm laser irradiations
SHG coefficients are KH2PO4(KDP) 32 times, its powder SHG coefficients are measured under 2.05 μm of laser irradiations as KTiOPO4(KTP) it is brilliant
2.0 times of body, and can realize phase matched.
As M=Na, Na2Ge(IO3)6Crystal exports very strong 532nm green lights, powder under 1064nm laser irradiations
SHG coefficients are KH2PO4(KDP) 15 times, its powder SHG coefficients are measured under 2.05 μm of laser irradiations as KTiOPO4(KTP) it is brilliant
0.8 times of body, and can realize phase matched.
According to the another aspect of the application, a kind of laser frequency converter is provided, which is characterized in that include any of the above-described nothing
Machine compound crystal and/or the inorganic compound being prepared according to any of the above-described method.
The advantageous effect of the application includes but not limited to：
(1) this application provides a kind of new inorganic compound, which shows strong frequency-doubled effect, powder
Last SHG coefficients are more than KH2PO4(KDP) 15 times, 32 times are reached as high as；Its powder SHG systems are measured under 2.05 μm of laser irradiations
Number is KTiOPO4(KTP) 2 or 0.8 times of crystal, and can realize phase matched, it is the nonlinear optical with potential using value
Learn material.
(2) inorganic compound provided herein has very high transmitance in 310~2500nm spectral regions,
UV cut-off wavelength is about 321nm.
(3) inorganic compound provided herein can be stabilized to 416 DEG C.
(4) present invention also provides the preparation methods of the inorganic compound crystal, and using hydrothermal crystallization method, growth obtains
Colourless M2Ge(IO3)6Crystal.The method process is simple, can obtain high-purity, high-crystallinity inorganic compound M2Ge
(IO3)6Crystalline material.
Description of the drawings
Fig. 1 is Li2Ge(IO3)6The crystal structure schematic diagram of crystal.
Fig. 2 is Na2Ge(IO3)6The crystal structure schematic diagram of crystal.
Fig. 3 is sample Li-1#The X-ray diffractogram being fitted according to the crystal structure that single crystal X-ray diffraction parses
Spectrum and sample 1#The collection of illustrative plates comparison that last X-ray diffraction of pulverizing is tested.
Fig. 4 is sample Na-1#The X-ray diffractogram being fitted according to the crystal structure that single crystal X-ray diffraction parses
Spectrum and sample 1#The collection of illustrative plates comparison that last X-ray diffraction of pulverizing is tested.
Fig. 5 is sample Li-1#Ultraviolet-visible-near-infrared diffusing reflection spectrum.
Fig. 6 is sample Na-1#Ultraviolet-visible-near-infrared diffusing reflection spectrum.
Fig. 7 is sample Li-1#Thermal multigraph.
Fig. 8 is sample Na-1#Thermal multigraph.
Specific embodiment
The application is described in detail, but the application is not limited to these embodiments with reference to embodiment.
Unless otherwise specified, raw materials and reagents used herein are all from commercially available, unprocessed direct use, used
Instrument and equipment uses the scheme and parameter of manufacturer's recommended.
1 sample Li-1 of embodiment#~sample Li-5#Preparation
Lithium source, ge source, propiodal and water are mixed into raw material according to certain molar ratio, are placed in the height of polytetrafluoroethyllining lining
Press in reaction kettle, then heat to crystallization temperature, at such a temperature constant temperature for a period of time after, with certain rate of temperature fall by system
Temperature is down to room temperature.After filtering and washing, colourless rodlike crystal prototype, the sample of as described inorganic compound crystal are obtained
Product.
Sample number into spectrum, raw material type and dosage, crystallization temperature and retention time, rate of temperature fall are as shown in table 1.
Table 1
2 sample Li-1 of embodiment#~sample Li-5#Crystallographic structural analysis
Using single crystal X-ray diffraction and powder x-ray diffraction method, to sample Li-1#~Li5#Carry out structure elucidation.
Wherein single crystal X-ray diffraction spreads out in U.S.'s Agilent (Agilent) company SuperNova CCD type X ray monocrystalline
It penetrates on instrument and carries out.Data collection temperature is 293K, and diffraction light sources are graphite monochromatised Mo-K alpha rays
Scan mode is ω -2 θ；Data carry out absorption correction processing using Multi-Scan methods.Structure elucidation uses SHELXTL-97
Program bag is completed；The position of heavy atom is determined with direct method, remaining atomic coordinates is obtained with poor Fourier synthetic method；With based on F2
The coordinate of all atoms of complete matrix least square method refine and anisotropy thermal parameter.
Powder x-ray diffraction is in the X-ray powder diffraction of the Miniflex II types of Rigaku Co., Ltd. (RIGAKU)
It is carried out on instrument, test condition is to fix target monochromatic source Cu-K α, wavelengthVoltage and current is 30kV/15A, is swept
Retouch 5~65 ° of range, 0.02 ° of scanning step.
Wherein, single crystal X-ray diffraction is the results show that sample 1#~5#Chemical formula is Li2Ge(IO3)6, belong to hexagonal crystal
System, space group P63, cell parameter is α=β=
90 °, γ=120 °.Its crystal structure is as shown in Figure 1, Fig. 1 is perspective view of the crystal structure along c-axis direction.As can be seen that
Li, a Ge there are one containing in each asymmetric cell, I and three O atom.Each Ge atoms are connected into 6 O atoms
GeO6Octahedron, and each I atoms connect to form IO with 3 O atoms3Pyrometric cone, 6 IO3Pyrometric cone is connected by monodentate ligand
In GeO6Octahedron forms the [Ge (IO of 0 dimension3)6]2-Anionic group.Li atoms are filled in [Ge (IO3)6]2-Anionic group it
Between gap in.It will be seen that IO from Fig. 13 -Being arranged along c-axis direction for middle lone pair electrons is basically identical.This arrangement
Mode is conducive to increase the polarity of compound, so as to enhance its nonlinear optical coefficients.
Powder x-ray diffraction is the results show that sample Li-1#~Li-5#On XRD spectra, peak position is essentially identical, various kinds
Product peak intensity slightly has difference.
With sample Li-1#For Typical Representative, belong to hexagonal crystal system, space group P63, cell parameter isα=β=90 °, γ=120 °, Z=
1.Its monocrystalline analysis result is as shown in table 2：
Table 2
With sample Li-1#For Typical Representative, as shown in figure 3, according to the crystal structure that its single crystal X-ray diffraction parses,
It is fitted obtained X ray diffracting spectrum and sample Li-1#It pulverizes the collection of illustrative plates that last X-ray diffraction is tested, peak position
It is consistent with peak intensity.Illustrate that gained sample has very high-purity.
3 sample Li-1 of embodiment#Frequency multiplication test experiments and result
With sample Li-1#For Typical Representative, to Li2Ge(IO3)6Carry out frequency multiplication test.
It is as follows：Using the Nd of the tune Q containing frequency converter:The wavelength that YAG solid state lasers generate respectively is
1064nm and 2.05 μm of laser irradiates tested crystal powder as fundamental frequency light, detected using photomultiplier caused by
Second harmonic, with oscilloscope display harmonic wave intensity.Crystal prototype to be measured is sifted out to the crystal of variable grain degree, particle with standard screen
Degree is respectively 25-45 μm, 45-53 μm, 53-75 μm, 75-105 μm, 105-150 μm, 150-210 μm, 210-300 μm.Observation times
Frequency signal judges whether it can realize phase matched with the variation tendency of granularity.It is more to be measured under similary test condition
The intensity of second harmonic caused by sample and reference crystal KH2PO4(KDP) and KTiOPO4(KTP) second harmonic caused by
Intensity, so as to obtain the relative size of sample frequency-doubled effect.
Test result shows:Compound L i2Ge(IO3)6Its powder SHG coefficients are KH under 1064nm laser irradiations2PO4
(KDP) 32 times, its powder SHG coefficients are measured under 2.05 μm of laser irradiations as KTiOPO4(KTP) 2 times of crystal, and can
Realize phase matched.
4 sample Li-1 of embodiment#Diffusing reflection absorption spectrum test
With sample Li-1#For Typical Representative, to Li2Ge(IO3)6Diffusing reflection absorption spectrum test is carried out, in the U.S.
It is carried out on Perkin-Elmer companies Lambda-950 types ultraviolet-visible-near infrared spectrometer.Crystal prototype is pulverized
End, with BaSO4As with reference to substrate.Test result is as shown in figure 5, show compound L i2Ge(IO3)6Crystal have it is wider
Through range, there is very high transmitance in 310~2500nm spectral regions, UV cut-off wavelength is about 321nm.
5 sample Li-1 of embodiment#Sample thermogravimetric analysis
With sample Li-1#For Typical Representative, to Li2Ge(IO3)62Thermogravimetric analysis is carried out, in the STA of German NETZSCH companies
It is carried out on 449F3 type thermogravimetric analyzers, the results are shown in Figure 7.As seen from the figure, Li2Ge(IO3)6Crystal, can stablize
To 416 DEG C.
6 sample Na-1 of embodiment#~sample Na-5#Preparation
Sodium source, ge source, propiodal and water are mixed into raw material according to certain molar ratio, are placed in the height of polytetrafluoroethyllining lining
Press in reaction kettle, then heat to crystallization temperature, at such a temperature constant temperature for a period of time after, with certain rate of temperature fall by system
Temperature is down to room temperature.After filtering and washing, the crystal prototype of colourless tabular, the sample of as described inorganic compound crystal are obtained
Product.
Sample number into spectrum, raw material type and dosage, crystallization temperature and retention time, rate of temperature fall are as shown in table 3.
Table 3
7 sample Na-1 of embodiment#~sample Na-5#Crystallographic structural analysis
Using single crystal X-ray diffraction and powder x-ray diffraction method, to sample Na-1#~Na-5#Carry out structure elucidation.
Wherein single crystal X-ray diffraction spreads out in U.S.'s Agilent (Agilent) company SuperNova CCD type X ray monocrystalline
It penetrates on instrument and carries out.Data collection temperature is 293K, and diffraction light sources are graphite monochromatised Mo-K alpha rays
Scan mode is ω -2 θ；Data carry out absorption correction processing using Multi-Scan methods.Structure elucidation uses SHELXTL-97
Program bag is completed；The position of heavy atom is determined with direct method, remaining atomic coordinates is obtained with poor Fourier synthetic method；With based on F2
The coordinate of all atoms of complete matrix least square method refine and anisotropy thermal parameter.
Powder x-ray diffraction is in the X-ray powder diffraction of the Miniflex II types of Rigaku Co., Ltd. (RIGAKU)
It is carried out on instrument, test condition is to fix target monochromatic source Cu-K α, wavelengthVoltage and current is 30kV/15A, is swept
Retouch 5~65 ° of range, 0.02 ° of scanning step.
Wherein, single crystal X-ray diffraction is the results show that sample Na-1#~Na-5#Chemical formula is Na2Ge(IO3)6, belong to six
Prismatic crystal system, space group P63, cell parameter is α=
β=90 °, γ=120 °, Z=1.Its crystal structure is as shown in Fig. 2, Fig. 2 is perspective view of the crystal structure along c-axis direction.
As can be seen that containing in each asymmetric cell, there are one Na, a Ge, I and three O atoms.Each Ge atoms and 6 O
Atom connects into GeO6Octahedron, and each I atoms connect to form IO with 3 O atoms3Pyrometric cone, 6 IO3Pyrometric cone passes through list
Tooth coordination is connected to GeO6Octahedron forms the [Ge (IO of 0 dimension3)6]2-Anionic group.Na atoms are filled in [Ge (IO3)6]2-It is cloudy
In gap between ionic group.It will be seen that IO from Fig. 23 -Middle lone pair electrons arrange basic one along c-axis direction
It causes.This arrangement mode is conducive to increase the polarity of compound, so as to enhance its nonlinear optical coefficients.
Powder x-ray diffraction is the results show that sample Na-1#~Na-5#On XRD spectra, peak position is essentially identical, various kinds
Product peak intensity slightly has difference.
With sample Na-1#For Typical Representative, belong to hexagonal crystal system, space group P63, cell parameter isα=β=90 °, γ=120 °, Z=
1.Its monocrystalline analysis result is as shown in table 4：
Table 4
With sample Na-1#For Typical Representative, as shown in figure 4, according to the crystal structure that its single crystal X-ray diffraction parses,
It is fitted obtained X ray diffracting spectrum and sample Na-1#It pulverizes the collection of illustrative plates that last X-ray diffraction is tested, peak position
It is consistent with peak intensity.Illustrate that gained sample has very high-purity.
8 sample Na-1 of embodiment#Frequency multiplication test experiments and result
With sample Na-1#For Typical Representative, to Na2Ge(IO3)6Carry out frequency multiplication test.
It is as follows：Using the Nd of the tune Q containing frequency converter:The wavelength that YAG solid state lasers generate respectively is
1064nm and 2.05 μm of laser irradiates tested crystal powder as fundamental frequency light, detected using photomultiplier caused by
Second harmonic, with oscilloscope display harmonic wave intensity.Crystal prototype to be measured is sifted out to the crystal of variable grain degree, particle with standard screen
Degree is respectively 25-45 μm, 45-53 μm, 53-75 μm, 75-105 μm, 105-150 μm, 150-210 μm, 210-300 μm.Observation times
Frequency signal judges whether it can realize phase matched with the variation tendency of granularity.It is more to be measured under similary test condition
The intensity of second harmonic caused by sample and reference crystal KH2PO4(KDP) and KTiOPO4(KTP) second harmonic caused by
Intensity, so as to obtain the relative size of sample frequency-doubled effect.
Test result shows:Compound N a2Ge(IO3)6Its powder SHG coefficients are KH under 1064nm laser irradiations2PO4
(KDP) 15 times, its powder SHG coefficients are measured under 2.05 μm of laser irradiations as KTiOPO4(KTP) 0.8 times of crystal, and all
It can realize phase matched.
9 sample Na-1 of embodiment#Diffusing reflection absorption spectrum test
With sample Na-1#For Typical Representative, to Na2Ge(IO3)6Diffusing reflection absorption spectrum test is carried out, in the U.S.
It is carried out on Perkin-Elmer companies Lambda-950 types ultraviolet-visible-near infrared spectrometer.Crystal prototype is pulverized
End, with BaSO4As with reference to substrate.Test result is as shown in fig. 6, show compound N a2Ge(IO3)6Crystal have it is wider
Through range, there is very high transmitance in 250~2500nm spectral regions, UV cut-off wavelength is about 267nm.
10 sample Na-1 of embodiment#Thermogravimetric analysis
With sample Na-1#For Typical Representative, to Na2Ge(IO3)6Thermogravimetric analysis is carried out, in German NETZSCH companies
It is carried out on STA449F3 type thermogravimetric analyzers, the results are shown in Figure 8.As seen from the figure, Na2Ge(IO3)6Crystal, Ke Yiwen
Determine to 410 DEG C.
The above is only several embodiments of the application, any type of limitation is not done to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, make a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in the range of technical solution.
Claims (10)
1. a kind of inorganic compound, which is characterized in that the chemical formula of the inorganic compound is：
M2Ge(IO3)6
Wherein, M is Li and/or Na；
The inorganic compound belongs to hexagonal crystal system, space group P63, cell parameter is α=β=90 °, γ=120 °, Z=1.
2. inorganic compound according to claim 1, which is characterized in that the UV absorption cut-off wave of the inorganic compound
It grows between 250~350nm.
3. inorganic compound according to claim 1, which is characterized in that M is Li in the chemical formula of the inorganic compound,
Cell parameter is α=β=90 °, γ=120 °, Z=1；
Or
M is Na in the chemical formula of the inorganic compound, and cell parameter is α=β=90 °, γ=120 °, Z=1.
4. the preparation method of any one of a kind of claims 1 to 3 inorganic compound, which is characterized in that using hydro-thermal legal system
Standby, by the raw mixture containing M element, Germanium, iodine and water, crystallization obtains under 180 DEG C~260 DEG C crystallization temperatures
It arrives；
In the raw mixture, the molal quantity of M element, the molal quantity of Germanium, the molal quantity of iodine and water volume ratio
For：
M：Ge：I：Water=1~10mol：1mol：1~20mol：1~50L；
Preferably, M：Ge：I：Water=5mol：1mol：2~10mol：1~5L.
5. according to the method described in claim 3, it is characterized in that, the crystallization temperature be 180 DEG C~250 DEG C, crystallization time
No less than 24 hours；
Preferably, the crystallization time is 24~260 hours.
6. the method according to claim 3 or 5, which is characterized in that in the raw mixture, M element carrys out self-contained lithiumation
Close object and/or compounds containing sodium；
Preferably, the lithium-containing compound is selected from least one of lithium nitrate, lithium chloride, lithium fluoride, lithia, lithium carbonate；
It is further preferred that the lithium salts is lithium carbonate；
Preferably, the compounds containing sodium is selected from least one of sodium nitrate, sodium chloride, sodium fluoride, sodium oxide molybdena, sodium carbonate；
It is further preferred that the lithium salts is sodium carbonate.
7. according to the method described in claim 3, it is characterized in that, in the raw mixture, Germanium is from nitric acid germanium, chlorine
Change at least one of germanium, germanium oxide；
Preferably, the Germanium comes from germanium oxide.
8. according to the method described in claim 3, it is characterized in that, in the raw mixture, iodine is from five oxidations two
At least one of iodine, acid iodide, periodic acid；
Preferably, the iodine comes from I2O5。
9. inorganic compound described in claims 1 or 2, the nothing being prepared according to any one of claim 3 to 8 the method
Application of at least one of the machine compound as non-linear optical crystal material.
10. a kind of laser frequency converter, which is characterized in that comprising described in claims 1 or 2 inorganic compound, according to power
Profit requires one kind in inorganic compound prepared by any one of 3 to 8 the methods.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN113802182B (en) * | 2020-06-15 | 2022-12-06 | 中国科学院福建物质结构研究所 | Inorganic compound crystal, preparation method and application thereof |
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