CN104018223B - Inorganic compound Na2Sn(IO3)6 as well as preparation method and application thereof - Google Patents
Inorganic compound Na2Sn(IO3)6 as well as preparation method and application thereof Download PDFInfo
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- CN104018223B CN104018223B CN201410263424.7A CN201410263424A CN104018223B CN 104018223 B CN104018223 B CN 104018223B CN 201410263424 A CN201410263424 A CN 201410263424A CN 104018223 B CN104018223 B CN 104018223B
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Abstract
This application involves a kind of inorganic compound Na2Sn (IO3) 6, preparation method and the usage. The chemical formula of the compound is Na2Sn (IO3) 6, belongs to hexagonal crystal system, space group P63, cell parameter is
α=β=90 °, γ=120 °, Z=1, unit cell volume are
6 crystal of colourless needles Na2Sn (IO3) is prepared using hydro-thermal method. The powder SHG effect of 6 crystal of Na2Sn (IO3) is 12 times of KH2PO4, and ultraviolet cut-on side is about 300nm.
Description
Technical field
The present invention relates to a kind of novel nonlinear optical crystal material.
Background technology
Nonlinear optical crystal is important photoelectric functional material, and the various quartz crystal devices that can be prepared as, such as doubler
Part, electrooptical switching, high speed photodetector part and holographic memory element etc., be widely used in field of photoelectric technology.Big measurer
The metal iodate having non-core structure shows the second-order nonlinear optical property of excellence, has attracted people to study widely emerging
Interest.Simple ternary iodate, as the seventies in last century begins to the α-HIO of research3、α-LiIO3And some new reports
NaI3O8、α-Cs2I4O11Deng, all show excellent second-order nonlinear optical property.In recent years, the research work of iodate is opened up
Wide to mixed metal quaternary iodate system, especially containing d0The mixed metal iodate of transition metal ions, and it is found that a large amount of new
The iodate nonlinear optical material of type, such as NaVO2(IO3)2(H2O)、K(VO)2O2(IO3)3、RbMoO3(IO3)、BaNbO
(IO3)5、Li2Ti(IO3)6、Na2Ti(IO3)6Deng, they all show extremely strong frequency-doubled effect.
The application widens the research of quaternary iodate further, first by Sn4+Ion is incorporated in iodate, it was found that new
The quaternary iodate Na of type2Sn(IO3)6, related work there is not yet document report so far.Na2Sn(IO3)6Show strong frequency multiplication
Effect and wide transparency range, be the novel nonlinear optical crystal material with using value.
Summary of the invention
For solving the problems referred to above, the application provides a kind of inorganic compound, it is characterised in that chemical formula is Na2Sn
(IO3)6, belonging to hexagonal crystal system, space group is P63, cell parameter is α=
β=90 °, γ=120 °, Z=1, unit cell volume is
Preferably, cell parameter isα=β
=90 °, γ=120 °, Z=1, unit cell volume is
Described inorganic compound Na2Sn(IO3)6Crystal structure as shown in Figure 1.Each Sn atom and 6 O atom connect
The SnO become6Octahedron, is connected, by each I atom and 3 O atom, the IO formed with six3Tetrahedron is connected shape by common summit
Become [Sn (IO3)6]2-Anionic units, [Sn (IO3)6]2-Anionic units passes through cation Na+Connect and form three dimensional structure.Should
[Sn(IO3)6]2-In anionic units, six IO3Group is all arranged in parallel along c-axis direction, and polarization is overlapped mutually.
The invention provides above-mentioned inorganic compound Na2Sn(IO3)6Preparation method, it is characterised in that use hydro-thermal
Prepared by method, after sodium source, Xi Yuan, propiodal and water being mixed, under 180～250 DEG C of crystallization temperatures, crystallization obtains.
Described sodium source, for the material containing sodium element；Described Xi Yuan, for the material containing tin element；Described propiodal, for containing
There is the material of I.Those skilled in the art, can select suitable sodium source, Xi Yuan, propiodal and join according to actual needs
Ratio.
Preferably, described sodium source, Xi Yuan, propiodal and water mixing molar ratio be sodium source: Xi Yuan: propiodal: water=0.5～
30:1:10～200:20～3000；Further preferred range be sodium source, Xi Yuan, propiodal and water mixing molar ratio be sodium
Source: Xi Yuan: propiodal: water=2～12:1:50～120:120～600；Wherein the molal quantity in sodium source is with sodium element contained therein
Molal quantity meter；The molal quantity of Xi Yuan is in terms of the molal quantity of tin element contained therein；The molal quantity of propiodal is with I contained therein
Molal quantity meter.
Preferably, described crystallization temperature is 220～240 DEG C, and crystallization time is no less than 20 hours.
Preferably, described crystallization time is 24～240 hours.
Preferably, described sodium source is optionally from sodium hydroxide, sodium carbonate, sodium nitrate, sodium oxide, sodium chloride, sodium iodate and fluorine
Change one or more in sodium.
Preferably, described sodium source is optionally from sodium hydroxide and/or sodium carbonate.
Preferably, one or more in described stannum source optional metals glass putty, stannum oxide and stannous chloride.
Preferably, described propiodal optionally one or both in iodic anhydride and iodic acid.
Described inorganic compound Na2Sn(IO3)6, can be used for preparing laser frequency converter part.
Described inorganic compound Na2Sn(IO3)6, can be used for realizing two frequencys multiplication of the laser beam that wavelength is 1.064 μm or
Frequency tripling harmonic wave.
The application also provides for a kind of laser frequency converter, it is characterised in that comprise described inorganic compound Na2Sn
(IO3)6。
The application also provides for a kind of laser frequency converter, it is characterised in that comprise the nothing prepared by any of the above-described method
Machine compound N a2Sn(IO3)6。
Preferably, described laser frequency converter, can be used for two frequencys multiplication or three of the laser beam that wavelength is 1.064 μm
Multiplied frequency harmonic exports.
Having the beneficial effect that of herein described technical scheme
Provide a kind of new compound N a2Sn(IO3)6, and the preparation method of this compound and purposes.Use hydro-thermal
Method, growth has obtained colourless Na2Sn(IO3)6Crystal.The wavelength utilizing the Nd:YAG laser instrument output adjusting Q is 1.064 μm
Laser carries out powder frequency doubling test as fundamental frequency light, shows compound N a2Sn(IO3)6Crystal has bigger frequency-doubled effect, about
For KH2PO4(KDP) 12 times of crystal, and phase matched can be realized.This frequency-doubled effect is about now widely used bbo crystal
Twice.It is wider through scope that ultraviolet-visible-near-infrared diffuse-reflectance spectrum test shows that this crystal has, and its UV-permeable cuts
Only limit is about 300nm (see Fig. 3).In view of the most preliminary test result, it is contemplated that compound N a2Sn(IO3)6Crystal is permissible
It is used for preparing two frequencys multiplication or the harmonic oscillator of frequency tripled laser output realizing Nd:YAG laser instrument, will lead in nonlinear optics
Territory obtains and is widely applied.Compound N a2Sn(IO3)6Crystal is it is also possible to lead in Electro-optical Modulation, Preset grating information processing etc.
Territory obtains important application.
In should be understood that in the range of herein disclosed technical scheme, above-mentioned each technical characteristic of the application and below
Can be combined with each other between each technical characteristic specifically described in (such as embodiment), thus constitute new or preferred technical side
Case.As space is limited, the most tired at this state.
According to technical scheme disclosed in the present application, those skilled in the art have the motivation needs according to actual production, pass through
Select Xi Yuan, sodium source and the kind of propiodal；Select suitable feedstock proportioning, crystallization temperature and crystallization time, to reach preferable skill
Art effect.
Unless otherwise defined, the meaning that all specialties used in literary composition are familiar with one skilled in the art with scientific words
Justice is identical.Additionally, any method similar or impartial to described content and material all can be applicable in the application method.Wen Zhong
Described preferable implementation only presents a demonstration with material and is used.
Accompanying drawing explanation
Fig. 1 is described inorganic compound Na2Sn(IO3)6Crystal structure schematic diagram.
Fig. 2 is the X ray diffracting spectrum of sample 1#；Wherein a is the crystal structure parsed according to single crystal X-ray diffraction,
The X ray diffracting spectrum that matching obtains；B is that sample 1# last X-ray diffraction of pulverizing tests the collection of illustrative plates that obtains.
Fig. 3 is that the diffuse-reflectance of sample 1# absorbs through spectrum.
Detailed description of the invention
Below in conjunction with embodiment, the application is expanded on further.Should be understood that these embodiments be merely to illustrate the application and not
For limiting scope of the present application.The experimental technique of unreceipted actual conditions in the following example, generally according to normal condition or
According to the condition proposed by manufacturer.
The preferred Na of inorganic compound is prepared as one2Sn(IO3)6Preferred embodiment, specifically comprise the following steps that former
Material NaOH, SnCl2With I2O5Being encapsulated in hydrothermal reaction kettle with watertight and carry out hydro-thermal reaction, reaction temperature is 180～250 DEG C, reaction
Time is 1～10 day, and then slow cooling is to 30 DEG C, and cooling rate is 0.5～150 DEG C/day, filters and cleans, can obtain nothing
The Na of color2Sn(IO3)6Crystal.Wherein raw material NaOH can be with Na2CO3Or NaF replaces, raw material SnCl2Sn powder or SnO can be used2Generation
Replace, raw material I2O5HIO can be used3Replace.
Embodiment 1 uses hydrothermal synthesis method synthesizing inorganic compound N a2Sn(IO3)6Crystal
Sodium source, Xi Yuan, propiodal and water are mixed according to a certain percentage, is sealed in the teflon-lined hydro-thermal of 25mL
In reactor, put in chamber type electric resistance furnace, under crystallization temperature after crystallization a period of time, through filtering, cleaning, be dried, obtain nothing
Color needle-like Na2Sn(IO3)6Crystal.Sodium source, Xi Yuan, the kind of propiodal, the proportioning of each raw material, crystallization temperature, crystallization time and sample
The relation of product numbering is as shown in table 1.
Table 1Na2Sn(IO3)6Synthesis condition and the relation of sample number into spectrum
aThe molal quantity in sodium source is in terms of the molal quantity of sodium element contained therein；The molal quantity of Xi Yuan is with tin element contained therein
Molal quantity meter；The molal quantity of propiodal is in terms of the molal quantity of I contained therein
Embodiment 2 inorganic compound Na2Sn(IO3)6Crystallographic structural analysis
Use single crystal X-ray diffraction and powder X-ray diffraction method, sample 1#～12# is carried out structure elucidation.
Wherein single crystal X-ray diffraction is enterprising at U.S. Agilent company SuperNova CCD type X-ray single crystal diffractometer
OK.Crystalline size is 0.09 × 0.07 × 0.04mm3；Data collection temperature is 293K, and diffraction light sources is graphite monochromatised Mo-
K alpha rayScan mode is ω-2 θ；Data acquisition Multi-Scan method carries out absorption correction process.
Structure elucidation uses SHELXTL-97 program bag to complete；Determine the position of heavy atom with direct method, obtain by difference Fourier synthetic method
To remaining atomic coordinates；With based on F2The coordinate of the complete matrix all atoms of method of least square refine and anisotropy thermal parameter.
Powder X-ray diffraction is carried out on the x-ray powder diffraction instrument of RIGAKU company of Japan Miniflex II type, surveys
Strip part is fixing target monochromater Cu-K α, wavelengthVoltage x current is 30kV/15A, slit DivSlit/
RecSlit/SctSlit is respectively 1.25deg/0.3mm/1.25deg, sweep limits 5-85 °, scanning step 0.02 °.
Wherein, single crystal X-ray diffraction result shows, sample 1#～12# chemical formula are Na2Sn(IO3)6, belong to six sides
Crystallographic system, P63Space group, cell parameter isα=β=90 °, γ=120 °, Z
=1, unit cell volume isIts crystal structure is as shown in Figure 1.
With sample 1# as Typical Representative, its crystal structural data is α=β=90 °, γ=120 °, Z=1, unit cell volume isSample 1#
Each atomic coordinates is as shown in table 2:
Each atomic coordinates, equivalent heat parameter and occupation rate in table 2 sample 1#
Wherein, powder X-ray diffraction result shows, sample 1#～12# is in XRD spectra, and peak position is essentially identical, various kinds
Product peak intensity slightly difference.
With sample 1# as Typical Representative, the crystal structure parsed according to its single crystal X-ray diffraction, the X that matching obtains penetrates
Ray diffraction diagram is composed and sample 1# pulverizes, and last X-ray diffraction tests the collection of illustrative plates obtained, and peak position is consistent with peak intensity.Say
Bright gained sample all has very high-purity.
Embodiment 3 frequency multiplication test experiments and result
The frequency multiplication test experiments of sample 1# is specific as follows: the wavelength using the Nd:YAG solid state laser adjusting Q to produce is
The laser of 1064nm, as fundamental frequency light, irradiates tested crystal powder, utilizes the two of the produced 532nm of photomultiplier tube detection
Subharmonic, by oscilloscope display harmonic wave intensity.Crystal prototype to be measured is ground with standard sample KDP crystal, sifts out with standard screen
The crystal of variable grain degree, granularity is respectively 25-45 μm, 45-53 μm, 53-75 μm, 75-105 μm, 105-150 μm, 150-
210μm、210-300μm.Observe the frequency-doubled signal variation tendency with granularity, it is judged that whether it can realize phase matched.?
Under same test condition, compare second harmonic produced by the intensity of second harmonic produced by sample and reference crystal KDP strong
Degree, thus obtain the relative size of sample frequency-doubled effect.
Test result shows compound N a2Sn(IO3)6Crystal has great frequency-doubled effect, about KH2PO4(KDP) crystal
12 times, and phase matched can be realized.
Embodiment 4 diffuse-reflectance absorption spectrum is tested
The diffuse-reflectance absorption spectrum test of sample 1# is in U.S.'s Perkin-Elmer company Lambda-950 type ultraviolet-can
See-near infrared spectrometer on carry out.Crystal prototype grind into powder, with BaSO4As with reference to substrate.Test result shows
Compound N a2Sn(IO3)6Having wider through scope, its ultraviolet cut-on limit is about 300nm (see Fig. 3).
The above, be only several embodiments of the present invention, and the present invention not does any type of restriction, although this
Bright with preferred embodiment disclose as above, but and be not used to limit the present invention, any those skilled in the art, do not taking off
In the range of technical solution of the present invention, utilize the technology contents of the disclosure above to make a little variation or modification is all equal to
Effect case study on implementation, in the range of belonging to technical scheme.
Claims (8)
1. the preparation method of an inorganic iodic acid stannum sodium crystal, it is characterised in that: the chemical formula of described inorganic iodic acid stannum sodium crystal
For Na2Sn(IO3)6, belonging to hexagonal crystal system, space group is P63, cell parameter is
α=β=90 °, γ=120 °, Z=1；
Described inorganic iodic acid stannum sodium crystal uses hydro-thermal method to prepare, after sodium source, Xi Yuan, propiodal and water being mixed, in 180～250
Under DEG C crystallization temperature, crystallization obtains；
Described sodium source, Xi Yuan, propiodal and water mixing molar ratio be sodium source: Xi Yuan: propiodal: water=0.5～30:1:10～
200:20～3000；
Wherein the molal quantity in sodium source is in terms of the molal quantity of sodium element contained therein；The molal quantity of Xi Yuan is with tin element contained therein
Molal quantity meter；The molal quantity of propiodal is in terms of the molal quantity of I contained therein.
Method the most according to claim 1, it is characterised in that described sodium source, Xi Yuan, propiodal and the molar ratio of water mixing
For sodium source: Xi Yuan: propiodal: water=2～12:1:50～120:120～600；
Wherein the molal quantity in sodium source is in terms of the molal quantity of sodium element contained therein；The molal quantity of Xi Yuan is with tin element contained therein
Molal quantity meter；The molal quantity of propiodal is in terms of the molal quantity of I contained therein.
Method the most according to claim 1, it is characterised in that described crystallization temperature is 220～240 DEG C, and crystallization time is not
Less than 20 hours.
Method the most according to claim 1, it is characterised in that described sodium source is optionally from sodium hydroxide, sodium carbonate, nitric acid
One or more in sodium, sodium oxide, sodium chloride, sodium iodate and sodium fluoride.
Method the most according to claim 1, it is characterised in that described Xi Yuan is optionally from metallic tin powder, stannum oxide and chlorination
One or more in stannous.
Method the most according to claim 1, it is characterised in that described propiodal optionally in iodic anhydride and iodic acid one
Plant or two kinds.
7. a laser frequency converter, it is characterised in that comprise by prepared by either method described in claim 1-6 is inorganic
Iodic acid stannum sodium crystal.
Laser frequency converter the most according to claim 7, it is characterised in that can be used for wavelength is swashing of 1.064 μm
Light light beam is with two frequencys multiplication or frequency tripling harmonic wave.
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| CN104611769B (en) * | 2015-02-11 | 2017-02-01 | 武汉大学 | Intermediate infrared nonlinear optical crystal material RbIO2F2 as well as preparation method and application of crystal material |
| CN106192001B (en) * | 2015-05-09 | 2018-05-11 | 中国科学院新疆理化技术研究所 | Caesium lead carbon oxygen iodine birefringece crystal and preparation method and purposes |
| CN106757343B (en) * | 2016-12-08 | 2019-05-28 | 中国科学院福建物质结构研究所 | A kind of novel nonlinear optical crystal Bi (IO3)F2Preparation and purposes |
| CN108070906A (en) * | 2017-12-15 | 2018-05-25 | 武汉大学 | Non-linear optical crystal of iodic acid germanium lithium and its preparation method and application |
| CN108221053A (en) * | 2018-02-08 | 2018-06-29 | 中国科学院福建物质结构研究所 | The preparation of novel nonlinear optical crystal and purposes |
| CN109137072B (en) * | 2018-10-08 | 2020-04-10 | 武汉大学 | Inorganic nonlinear optical crystal sodium bismuth iodate and preparation and application thereof |
| CN109913952B (en) * | 2019-03-20 | 2020-10-02 | 同济大学 | Bismuth iodate and selenate infrared frequency doubling crystal material and preparation and application thereof |
| CN110306240B (en) * | 2019-07-26 | 2020-10-09 | 中国科学院新疆理化技术研究所 | Non-linear optical crystal of sodium potassium iodate and its preparation method and use |
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