CN105463578A - Infrared nonlinear optical crystal material as well as preparation method and application thereof - Google Patents
Infrared nonlinear optical crystal material as well as preparation method and application thereof Download PDFInfo
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- 230000003287 optical effect Effects 0.000 title claims abstract description 55
- 239000013078 crystal Substances 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- 239000000523 sample Substances 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 7
- 150000003624 transition metals Chemical group 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000003836 solid-state method Methods 0.000 claims description 6
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 5
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 4
- 150000008045 alkali metal halides Chemical class 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 238000003384 imaging method Methods 0.000 claims description 3
- 230000010365 information processing Effects 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002178 crystalline material Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- 239000002184 metal Substances 0.000 abstract description 6
- 239000000843 powder Substances 0.000 abstract description 6
- 239000012612 commercial material Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 238000002834 transmittance Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 9
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002447 crystallographic data Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910000928 Yellow copper Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
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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
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- 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
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01D—MEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
- G01D5/00—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable
- G01D5/26—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable characterised by optical transfer means, i.e. using infrared, visible, or ultraviolet light
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
- H01S3/16—Solid materials
- H01S3/1601—Solid materials characterised by an active (lasing) ion
- H01S3/162—Solid materials characterised by an active (lasing) ion transition metal
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- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Metallurgy (AREA)
- Electromagnetism (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention relates to an infrared nonlinear optical crystal material. The infrared nonlinear optical crystal material has the molecular formula as follows: AX4X'5Te12, wherein A refers to an alkali metal element, X refers to a transition metal element, and X' refers to an IIIA family metal element. The crystal structure of the infrared nonlinear optical crystal material belongs to a trigonal system, and the space group is R3. The novel infrared nonlinear optical crystal material has the excellent second-order nonlinear optical properties, the wider light transmittance range and the high infrared doubled-frequency response, and the powder doubled-frequency strength of the material can be 2-9 times that of a commercial material AgGaS2, so that the material can be applied to mid-infrared detectors and lasers. Besides, the method for preparing the infrared nonlinear optical crystal material is simple to operate, and an obtained sample has higher crystallinity and purity.
Description
Technical field
The present invention relates to Inorganic Nonlinear Optical Materials technical field, in particular to a kind of infrared nonlinear optical crystal material, preparation method and infrared eye prepared therefrom or infrared laser.
Background technology
Non-linear optical effect derives from the interaction between laser and medium, when laser can produce non-linear optical effect when having the Propagation of second order susceptibility of non-zero, as difference frequency and frequently, frequency multiplication and parameter amplification etc.Utilize the second order nonlinear optical effect of non-heart crystal can make the device for non-linear optical such as frequency converter, second harmonic generator, optical parametric oscillator, and the continuously adjustable laser of wavelength can be obtained.The non-linear optic crystal of existing market is substantially all inorganic materials, according to the difference of its application band, can be divided into ultraviolet band, Visible-to-Near InfaRed wave band and mid and far infrared wave band three major types.The non-linear optical crystal material of its medium ultraviolet and visible waveband can meet the requirement of practical application.
The non-linear optical crystal material mainly ABC of infrared band
2the semiconductor material of the yellow copper structure of type, such as AgGaS
2, AgGaSe
2, ZnGeP
2deng, the outstanding advantages of this compounds is that nonlinear optical coefficients are large and mid and far infrared transmitance is high, but also has some serious shortcomings, and such as damage threshold is low, there is two-photon absorption etc., thus limits their application.And the non-linear optical crystal material of mid and far infrared has important application in resource detection, space technology and communication etc.
Therefore a difficult point and focus that novel mid and far infrared non-linear optical crystal material is current nonlinear optical material research field is explored.And the mid and far infrared non-linear optical crystal material major part of the chalcogen reported at present concentrates on sulfide and selenide.The compound of Te is the frontier of a rare developing.
Summary of the invention
The present invention aims to provide a kind of infrared nonlinear optical crystal material and its preparation method and application, and this optical crystal material has excellent Nonlinear Second order Optical Properties and magnetic property, and its powder frequency doubling intensity can reach commercial material AgGaS
22 ~ 9 times.
To achieve these goals, the invention provides a kind of infrared nonlinear optical crystal material, it has molecular formula as follows: AX
4x'
5te
12.Wherein, A is alkali metal; X is transition metal; X' is IIIA race metallic element.
Fig. 1 shows AX
4x'
5te
12crystalline structure, can find out, the crystalline structure of this infrared nonlinear optical crystal material belongs to trigonal system, and spacer is R3.Its structure is mainly by MTe
4three-dimensional " diamond-like stone-type " skeleton structure that (M=X/X ' jointly occupy) tetrahedron is interconnected to form by sharing summit, basic metal A is filled among three dimensional skeletal structure.
According to the present invention, A can be preferably Rb and/or Cs.X be selected from IIB race metallic element and VIIB race metallic element one or more.Such as X can be one or more in Zn, Cd and Mn.Preferred X' can be Ga or In.
According to the present invention, the molecular formula of crystalline material can be RbMn
4ga
5te
12, CsMn
4ga
5te
12, RbCd
4ga
5te
12, CsMn
4in
5te
12, CsZn
4in
5te
12, CsCd
4in
5te
12, CsCd
4ga
5te
12, RbZn
4ga
5te
12, CsZn
4ga
5te
12, RbZn
4in
5te
12, RbCd
4in
5te
12and RbMn
4in
5te
12in one.
Preferably, the unit cell parameters of non-linear optical crystal material can be
α=β=90, γ=120 °.Further preferably, the unit cell parameters of non-linear optical crystal material can be such as
α=β=90, γ=120 °.
Present invention also offers a kind of preparation method of above-mentioned infrared nonlinear optical crystal material, comprise: alkali metal halide AR, transition metal X, IIIA race metallic element X' and simple substance tellurium are mixed, prepares infrared nonlinear optical crystal material by high temperature solid-state method.
According to the present invention, described A can be Rb and/or Cs.X be selected from IIB race metallic element and VIIB race metallic element one or more.Such as X can be preferably one or more in Zn, Cd and Mn.X' is preferably Ga and/or In.
According to the present invention, alkali metal halide AR (R represents halogen), transition metal X, IIIA race metallic element X' and simple substance tellurium are preferably AR:X:X':Te=(1.1 ~ 6.0): 4:5:12 according to mol ratio, are more preferably AR:X:X':Te=(1.5 ~ 5.0): 4:5:12.Wherein R can be Cl, Br or I.
Such as, can be AR according to mol ratio raw material: transition metal Zn or Cd: metal X ': simple substance Te=5:4:5:12; Or can be AR: transient metal Mn: metal X ': simple substance Te=1.5:4:5:12.
Particularly, such as mol ratio can be RbCl:Mn:Ga:Te=1.5:4:5:12; Or CsCl:Mn:Ga:Te=1.5:4:5:12; Or RbCl:Cd:Ga:Te=5:4:5:12; Or CsCl:Mn:In:Te=1.5:4:5:12; Or CsCl:Zn:In:Te=5:4:5:12; Or CsCl:Cd:In:Te=5:4:5:12.
According to the present invention, described high temperature solid-state method is by described raw material at high temperature held for some time, at preferably raw mixture being placed in 750 ~ 1300 DEG C, and more preferably 800 ~ 1100 DEG C, such as 900-1000 DEG C.Soaking time is no less than 30 hours, is preferably no less than 50 hours, and more preferably insulation is no less than 100 hours.Such as, be incubated 100 hours at can being placed in 950 DEG C, or be incubated 100 hours at such as can being placed in 1000 DEG C.Described high temperature solid-state method preferably carries out under vacuum.
According to the present invention, in the above-mentioned methods, also comprise the step of the cooling of the product after by heating and thermal insulation after preparation, after being preferably cooled to 300 DEG C with the speed being no more than 5 DEG C/h, be cooled to room temperature.After cooling, preferably by product washing, drying, obtain infrared nonlinear optical crystal material.Described washing preferably uses water (such as deionized water).Described drying such as can use ethanol to carry out drying.
Infrared nonlinear optical crystal material of the present invention has excellent Nonlinear Second order Optical Properties, and it has significant application value in high-tech areas such as laser frequency conversion, near infrared probe, Preset grating information processing, terahertz imagings.
Invention further provides the purposes of described infrared nonlinear optical crystal material, it can be applicable to infrared eye, infrared laser, laser frequency conversion, near infrared probe, Preset grating information processing, terahertz imaging etc.
Invention further provides a kind of infrared eye, it contains any one infrared nonlinear optical crystal material above-mentioned.
Invention further provides a kind of infrared laser, it contains any one infrared nonlinear optical crystal material above-mentioned.
The application at least has following beneficial effect:
The invention provides a kind of novel infrared nonlinear optical crystal material, it has excellent Nonlinear Second order Optical Properties, and its energy gap is greater than 1.45eV, has wider transparency range, and have strong frequency multiplication response, its powder frequency doubling intensity can reach commercial material AgGaS
22 ~ 9 times, can be used for infrared eye and laser apparatus.In addition, the method for what the application provided prepare infrared nonlinear optical crystal material is simple to operate, and the sample obtained has higher degree of crystallinity and purity.
Accompanying drawing explanation
Fig. 1 is AX
4x'
5te
12crystalline structure schematic diagram.
Fig. 2 is AX
4x'
5te
12the X ray diffracting spectrum of middle sample 1# ~ 6#.
Fig. 3 is AX
4x'
5te
12the crystal FT-IR spectrum of middle sample 1# ~ 6#.
Fig. 4 is AX
4x'
5te
12the graph of a relation of the crystal powder frequency multiplication intensity reference of middle sample 4# ~ 6# and AGS (46 – 74 μm).
Embodiment
Below by way of exemplary specific embodiment, technical scheme of the present invention is described in detail.But these embodiments should be interpreted as limiting the scope of the invention.All technology realized based on foregoing of the present invention are all encompassed in the present invention and are intended in the scope of protection.
Except as otherwise noted, described in embodiment raw material and reagent are commercially available prod.
Embodiment 1
By ACl, metal X, metal X ' and simple substance tellurium mix according to a certain percentage, obtain raw material.Raw material is put into quartz crucible, and the quartz crucible that raw material is housed is placed in crystal reaction tube, and vacuum is evacuated to 10
-2pa also seals crystal reaction tube with oxyhydrogen flame scorification.Crystal reaction tube is put into the tube furnace with temperature controller, be heated to solid melting temperatur, and keep for some time.Then after being cooled to 300 DEG C with the speed program being no more than 5 DEG C/h, stopping heating, naturally cool to room temperature, product is also dry with ethanol by deionized water wash, obtains infrared nonlinear optical crystal material.
Sample number into spectrum, proportioning raw materials, solid melting temperatur and hold-time are as shown in table 1.
Table 1
The structural characterization of sample
The X – ray single crystal diffraction of sample 1# ~ 6# carries out on MercuryCCD type single crystal diffractometer, Mo target, K α source of radiation (λ=0.07107nm), probe temperature 293K.And by Shelxtl97, structure elucidation is carried out to it.The crystallographic data result of each sample is as shown in table 2, and crystalline structure schematic diagram as shown in Figure 1.
The crystallographic data of table 2 sample 1# ~ 6#
Can find out, sample 1# ~ 6# has identical crystalline structure, and structure is mainly by MTe
4(M=X/X
'jointly occupying) tetrahedron is by sharing three-dimensional " diamond-like stone-type " skeleton structure that is interconnected to form of summit, and basic metal A is filled among three dimensional skeletal structure.
The X-ray powder diffraction material phase analysis (XRD) of sample 1# ~ 6# carries out on the MiniFlexII type X-ray diffractometer of Rigaku company, Cu target, K α source of radiation (λ=0.154184nm).The XRD spectra that the powder X-ray RD figure of sample 1# ~ 6# and single crystal diffraction data fitting obtain as shown in Figure 2.As seen from Figure 2, the XRD figure of sample 1# ~ 6# is consistent with the XRD spectra that single crystal diffraction data fitting obtains, and illustrates that gained sample has very high degree of crystallinity and purity.
The optical property of sample characterizes
The optical property of sample 1# ~ 6# absorbs at Perkin-ElmerFT-IR infrared spectrometer and Perkin-ElmerLambda900 UV, visible light (near infrared) or the spectrometer that diffuses characterizes, and result is as shown in table 3.As shown in Figure 3, frequency doubling property as shown in Figure 4 for the light transmission of sample 1# ~ 6#.As can be seen from Figure 3 powdered sample does not absorb substantially in whole test specification, illustrates that powdered sample has wider transparency range.As can be seen from Figure 4, illustrate that 4#-6# sample has strong powder frequency doubling intensity.
The optical performance data of table 3 sample 1# ~ 6#
* reference and AGS (46 ~ 74 μm), laser wavelength of incidence is 2050nm.
The above, only several embodiments of the application, not any type of restriction is done to the application, although the application discloses as above with preferred embodiment, but and be not used to limit the application, any those skilled in the art, not departing from the scope of technical scheme, utilize the technology contents of above-mentioned announcement to make a little variation or modify and be all equal to equivalent case study on implementation, all belong within the scope of technical scheme.
Claims (10)
1. an infrared nonlinear optical crystal material, has molecular formula as follows: AX
4x'
5te
12;
Wherein, A is alkali metal; X is transition metal; X' is IIIA race metallic element;
Preferably, the crystalline structure of described infrared nonlinear optical crystal material belongs to trigonal system, and spacer is R3.
2. infrared nonlinear optical crystal material according to claim 1, is characterized in that,
Described A is Rb and/or Cs;
Described X be selected from IIB race metallic element and VIIB race metallic element one or more, be preferably in Zn, Cd and Mn one or more;
Described X' is Ga and/or In.
3. infrared nonlinear optical crystal material according to claim 1 and 2, is characterized in that,
Unit cell parameters is
α=β=90, γ=120 °.
4. infrared nonlinear optical crystal material according to claim 3, is characterized in that,
Unit cell parameters is
α=β=90, γ=120 °.
5. the infrared nonlinear optical crystal material according to any one of claim 1-4, is characterized in that, the molecular formula of described crystalline material is selected from RbMn
4ga
5te
12, CsMn
4ga
5te
12, RbCd
4ga
5te
12, CsMn
4in
5te
12, CsZn
4in
5te
12, CsCd
4in
5te
12, CsCd
4ga
5te
12, RbZn
4ga
5te
12, CsZn
4ga
5te
12, RbZn
4in
5te
12, RbCd
4in
5te
12and RbMn
4in
5te
12in one.
6. a preparation method for the infrared nonlinear optical crystal material described in any one of claim 1-5, comprising:
Alkali metal halide AR (R represents halogen), transition metal X, IIIA race metallic element X' and simple substance tellurium are mixed, prepares infrared nonlinear optical crystal material by high temperature solid-state method;
Preferably, alkali metal halide AR, transition metal X, IIIA race metallic element X' and simple substance tellurium mol ratio are AR:X:X':Te=(1.1 ~ 6.0): 4:5:12; Be more preferably AR:X:X':Te=(1.5 ~ 5.0): 4:5:12.
7. preparation method according to claim 6, is characterized in that,
Described high temperature solid-state method is at described raw mixture is placed in 750 ~ 1300 DEG C, preferably 800 ~ 1100 DEG C, such as 900 ~ 1000 DEG C;
Soaking time is no less than 30 hours, and preferably insulation is no less than 50 hours, and more preferably insulation is no less than 100 hours;
Such as, be incubated 100 hours at can being placed in 950 DEG C, or be incubated 100 hours at 1000 DEG C can be placed in;
Described high temperature solid-state method preferably carries out under vacuum.
8. the purposes of the infrared nonlinear optical crystal material described in any one of claim 1-5, is characterized in that, it can be used for infrared eye, infrared laser, laser frequency conversion, near infrared probe, Preset grating information processing or terahertz imaging.
9. an infrared eye, is characterized in that, comprises the infrared nonlinear optical crystal material described in any one of claim 1 to 5.
10. an infrared laser, is characterized in that, it comprises the infrared nonlinear optical crystal material described in any one of claim 1 to 5.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106087063A (en) * | 2016-08-23 | 2016-11-09 | 中国科学院福建物质结构研究所 | Infrared nonlinear optical crystal CsZn4ga5s12and its production and use |
| CN106119969A (en) * | 2016-08-23 | 2016-11-16 | 中国科学院福建物质结构研究所 | Optical crystal AZn4ga5s12purposes as FTIR radiation transmittance |
| CN106757364A (en) * | 2016-11-29 | 2017-05-31 | 中国科学院福建物质结构研究所 | Infrared nonlinear optical crystal material AZn4In5Se12And its production and use |
| CN106757365A (en) * | 2016-12-06 | 2017-05-31 | 中国科学院福建物质结构研究所 | A kind of crystalline material, its preparation method and the nonlinear optical crystal comprising it |
| WO2017201648A1 (en) * | 2016-05-23 | 2017-11-30 | 中国科学院福建物质结构研究所 | Infrared nonlinear optical crystal material, and preparation method therefor and use thereof |
| CN109097835A (en) * | 2017-08-31 | 2018-12-28 | 中国科学院理化技术研究所 | KHg4Ga5Se12Nonlinear optical crystal, preparation method thereof and nonlinear optical device |
| CN115305575A (en) * | 2021-05-06 | 2022-11-08 | 中国科学院上海硅酸盐研究所 | Infrared nonlinear optical crystal material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024899A (en) * | 2006-02-21 | 2007-08-29 | 中国科学院福建物质结构研究所 | Non-linear optical crystal selenium borate |
| CN103031607A (en) * | 2012-12-12 | 2013-04-10 | 中国科学院福建物质结构研究所 | Infrared nonlinear optical crystal AB4C5Se12 |
-
2015
- 2015-12-10 CN CN201510915491.7A patent/CN105463578A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024899A (en) * | 2006-02-21 | 2007-08-29 | 中国科学院福建物质结构研究所 | Non-linear optical crystal selenium borate |
| CN103031607A (en) * | 2012-12-12 | 2013-04-10 | 中国科学院福建物质结构研究所 | Infrared nonlinear optical crystal AB4C5Se12 |
Non-Patent Citations (2)
| Title |
|---|
| H. SCHWER等: "Crystal structure and twinning of KCd4Ga5S12 and some isotypic AB4C5X12 compounds", 《ZEITSCHRIFT FÜR KRISTALLOGRAPHIE》 * |
| HUA LIN等: "Functionalization Based on the Substitutional Flexibility: Strong Middle IR Nonlinear Optical Selenides AXII4XIII5Se12", 《J. AM. CHEM. SOC.》 * |
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| WO2017201648A1 (en) * | 2016-05-23 | 2017-11-30 | 中国科学院福建物质结构研究所 | Infrared nonlinear optical crystal material, and preparation method therefor and use thereof |
| CN106087063A (en) * | 2016-08-23 | 2016-11-09 | 中国科学院福建物质结构研究所 | Infrared nonlinear optical crystal CsZn4ga5s12and its production and use |
| CN106119969A (en) * | 2016-08-23 | 2016-11-16 | 中国科学院福建物质结构研究所 | Optical crystal AZn4ga5s12purposes as FTIR radiation transmittance |
| CN106757364A (en) * | 2016-11-29 | 2017-05-31 | 中国科学院福建物质结构研究所 | Infrared nonlinear optical crystal material AZn4In5Se12And its production and use |
| CN106757365A (en) * | 2016-12-06 | 2017-05-31 | 中国科学院福建物质结构研究所 | A kind of crystalline material, its preparation method and the nonlinear optical crystal comprising it |
| CN106757365B (en) * | 2016-12-06 | 2019-07-30 | 中国科学院福建物质结构研究所 | A kind of crystalline material, preparation method and the nonlinear optical crystal comprising it |
| CN109097835A (en) * | 2017-08-31 | 2018-12-28 | 中国科学院理化技术研究所 | KHg4Ga5Se12Nonlinear optical crystal, preparation method thereof and nonlinear optical device |
| CN115305575A (en) * | 2021-05-06 | 2022-11-08 | 中国科学院上海硅酸盐研究所 | Infrared nonlinear optical crystal material and preparation method and application thereof |
| CN115305575B (en) * | 2021-05-06 | 2023-12-08 | 中国科学院上海硅酸盐研究所 | Infrared nonlinear optical crystal material and preparation method and application thereof |
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