CN105603531A - Mid-infrared nonlinear optical crystal, preparation method and applications thereof - Google Patents
Mid-infrared nonlinear optical crystal, preparation method and applications thereof Download PDFInfo
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- CN105603531A CN105603531A CN201410658470.7A CN201410658470A CN105603531A CN 105603531 A CN105603531 A CN 105603531A CN 201410658470 A CN201410658470 A CN 201410658470A CN 105603531 A CN105603531 A CN 105603531A
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Abstract
This application discloses a kind of nonlinear crystalline material, preparation method and applications responded with strong infrared frequency multiplication. Its nonlinear crystalline material has molecular formula as follows: Ba4MGa4Se10Cl2 is wherein, M is metallic element, is made of selected from least one of Group IIB metal element, VIIB race metallic element, group VIII metal element or M at least one of at least one of IB race metallic element and Group IIIA metallic element; The crystal belongs to tetragonal crystal system, and space group is
The powder frequency doubling intensity of material can reach 59 times of commercial material AgGaS2, can be used for that photoelectronic warfare, resource detection, space be anti-ballistic and communication etc..
Description
Technical field
The application relates to infrared non-linear optical material Complex Function multi-functional in a kind of can realizationMaterial and preparation method thereof, belongs to Inorganic Nonlinear Optical Materials field.
Background technology
Nonlinear optical crystal shows the above nonlinear optical effect of secondary for laser highfieldCrystal. It has the nonlinear opticses such as laser freuqency doubling, difference frequency, many times frequency multiplication, parametric oscillation and amplificationEffect, laser technology, military affairs and civilian on brought into play more and more important effect.
According to its transmission region scope, nonlinear optical crystal can be divided into ultraviolet, visible and infrared light districtThree major types. Wherein, the crystal of some ultraviolets and visual field is (as KH2PO4(KDP),KTiOPO4(KTP),β-BaB2O4(BBO),LiB3O5(LBO)) all have excellent optical property andBe widely used in practice.
The commercial material of existing infrared non-linear is (as ZnGeP2，AgGaS2，LiGaS2，LiInS2)All there is the low grade of laser damage threshold defect separately, can not meet growing practical application needAsk. And middle-infrared band (2-20 μ is m) the important wave band of telecommunication, middle infrared non-linear opticsCrystal has important application at optoelectronic areas, as passed through optical parametric oscillation or optical parameter amplification etc.Means can extend to middle infrared by the laser of near infrared band; Important laser to mid-infrared light district entersRow frequency multiplication, thus the continuously adjustable laser of wavelength etc. obtained. So middle infrared non-linear optics (NLO)There is important application the aspects such as material is anti-ballistic at photoelectronic warfare, resource detection, space, communication.
Therefore the novel middle infrared nonlinear optical crystal material of finding or explore synthetic premium properties isOne of the difficult point of current nonlinear optical material research field and focus. And middle infrared non-linear optics crystalline substanceThe Complex Function of body is the frontier of a rare developing especially.
The application is by the three-dimensional anion frame compd B of the T1-T2 to having reported for work a3CsGa5Se10Cl2(J.Am.Chem.Soc., 2012,134,2227 – 2235) implement the collaborative replacement of effective double ion,Successfully obtain a kind of noval chemical compound Ba with strong infrared frequency multiplication response4MGa4Se10Cl2(M＝Zn, Cd, Mn, Cu/Ga). Keeping on the constant basis of crystal framework structure, with different transition goldBelong to and replace the tetrahedral metal center of T1, compd B a4MGa4Se10Cl2Realize function Composite.The collaborative design that replaces the tactful multifunctional composite for functional direction of this effective double ion is closedOne-tenth and performance regulation and control provide new thinking and direction.
Summary of the invention
According to the application aspect, provide a kind of non-linear crystalline substance with strong infrared frequency multiplication responseBody material, this nonlinear crystalline material not only has good Nonlinear Second order Optical Properties, also hasPhotoluminescent property, its powder frequency doubling intensity can reach commercial materials A gGaS230～59 times.
This nonlinear crystalline material is characterised in that to have molecular formula as follows:
Ba4MGa4Se10Cl2
Wherein, M is metallic element, is selected from IIB family metallic element, VIIB family metallic element, VIIIAt least one in family's metallic element or M are by least one and IIIA family gold in IB family metallic elementBelong at least one composition in element; The crystal structure of described nonlinear crystalline material belongs to tetragonalSystem, space group is
Preferably, described IIB family metallic element is Zn, Cd.
Preferably, described VIIB group metallic element is Mn.
Preferably, described VIII family metallic element is Fe, Co.
Preferably, described IB family metallic element is Cu.
Preferably, described IIIA family metallic element is Ga.
Preferably, the cell parameter of described non-linear optical crystal material is α＝β＝γ＝90°。
Preferably, the cell parameter of described non-linear optical crystal material isα＝β＝γ＝90°。
Preferably, the molecular formula of described crystalline material is selected from Ba4ZnGa4Se10Cl2、Ba4CdGa4Se10Cl2、Ba4MnGa4Se10Cl2、Ba4Cu0.5Ga4.5Se10Cl2、Ba4FeGa4Se10Cl2、Ba4CoGa4Se10Cl2In at least one.
Preferably, the molecular formula of described crystalline material is selected from Ba4ZnGa4Se10Cl2、Ba4CdGa4Se10Cl2、Ba4MnGa4Se10Cl2、Ba4Cu0.5Ga4.5Se10Cl2In at least one.Wherein, Ba4Cu0.5Ga4.5Se10Cl2Can also be expressed as Ba4Cu0.5Ga0.5Ga4Se10Cl2。
As shown in Figure 1, its structure is mainly by symmetry for the crystal structure of described nonlinear crystalline materialThe three dimensional network structure that the super tetrahedron of T1 tetrahedron and T2 is alternately interconnected to form by sharing Se,Ba2+And Cl-Be filled among the cavity of three-dimensional grid. Wherein T1 is MSe4 6-Tetrahedron, T2 isBy four GaSe4 5-Super tetrahedron [the Ga that tetrahedron forms4Se10]8-。
Described nonlinear crystalline material, except having good Nonlinear Second order Optical Properties, also has glimmeringLight property. For example, compd B a4Cu0.5Ga4.5Se10Cl2Under 2.05 μ m laser excitations, its powderFrequency multiplication intensity is AgGaS2(can be abbreviated as AGS) 39 times. Ba4Cu0.5Ga4.5Se10Cl2TransmittingWavelength (λem=880nm) with the Compound Phase of isomorphism than extending to closely red from visible ruddiness regionExterior domain. Expect that it sells off information processing at laser frequency conversion, Electro-optical Modulation, light, near-infrared is visitedThe high-tech areas such as pin (can be used for bio-imaging) have significant application value.
According to the application's another aspect, the preparation method of described non-linear optical crystal material is provided,It is characterized in that, will contain BaCl2, barium metal, metal M, gallium and simple substance selenium raw material putUnder vacuum condition, adopt high temperature solid-state method to prepare described non-linear optical crystal material.
Preferably, BaCl in described raw material2, the rubbing of barium metal, metal M, gallium and simple substance seleniumYour ratio is BaCl2: barium metal: metal M: gallium: simple substance selenium=1:3:1:4:10.
Preferably, described high temperature solid-state method, for raw material is placed at 870～1100 DEG C, keeps being no less than50 hours.
Preferably, described high temperature solid-state method, for raw material is placed at 870～1100 DEG C, keeps being no less than100 hours; Then be cooled to after 300 DEG C to be no more than the speed program of 5 DEG C/h, be cooled to chamberTemperature, obtains described non-linear optical crystal material.
According to one preferred embodiment, the preparation method of described non-linear optical crystal material, itsBe characterised in that, at least containing having the following steps:
(a) by BaCl2, barium metal, metal M, gallium and simple substance selenium according to molar ratio isBaCl2: barium metal: metal M: gallium: the ratio of simple substance selenium=1:3:1:4:10 is mixed allEven, obtain raw material;
(b) step (a) gained raw material is placed in to container, sealed after being vacuumized container;
(c) closed container that raw material is housed is placed in to heater, is warming up to 870～1100 DEG C,Keep after at least 100 hours, stop being no more than after the speed program of 5 DEG C/h is cooled to 300 DEG CHeating, naturally cools to room temperature and obtains described non-linear optical crystal material.
Described preparation method's principle is the three-dimensional anion frame of the T1-T2 by applicant has been reported for workCompd B a3CsGa5Se10Cl2Implement the collaborative replacement of effective double ion, refer to Fig. 2. Utilize thisThe effectively collaborative strategy that replaces of double ion, by the BaCl of stoichiometric proportion2With simple substance Ba, M, Ga,Se is blended under high temperature solid-state synthesis condition and obtains target product.
The introducing of new metallic element, has realized the Composite of crystalline material function. For example, the application instituteState Ba in nonlinear crystalline material4Cu0.5Ga4.5Se10Cl2Second nonlinear and T1-T2 skeleton are realizedEmission wavelength expands to the compound of near infrared region from ruddiness region; Ba4MnGa4Se10Cl2RealizeSecond nonlinear, the function of red emission and magnetic is compound.
According to the application's another aspect, Infrared Detectors in one is provided, it is characterized in that, containThe nonlinear optics that above-mentioned arbitrary non-linear optical crystal material and/or above-mentioned either method prepareCrystalline material.
According to the application's another aspect, a kind of middle infrared laser is provided, it is characterized in that, containThe nonlinear optics that above-mentioned arbitrary non-linear optical crystal material and/or above-mentioned either method prepareCrystalline material.
The application has following beneficial effect:
(1) the application provides a kind of novel middle infrared nonlinear optical crystal, this nonlinear crystalMaterial not only has good Nonlinear Second order Optical Properties, also has photoluminescent property, its powder frequency doublingIntensity can reach commercial materials A gGaS259 times.
(2) the application provides the method for preparing above-mentioned middle infrared nonlinear optical crystal material. ProfitReplace the synthetic crystalline material with complex function with effective double ion is collaborative.
(3) nonlinear crystalline material that the application provides has good second nonlinear opticMatter, can be used for middle Infrared Detectors and laser instrument.
Brief description of the drawings
Fig. 1 is Ba4MGa4Se10Cl2Crystal structure schematic diagram.
Fig. 2 is Ba3CsGa5Se10Cl2Collaborative replacement of double ion, generates Ba4MGa4Se10Cl2PrincipleFigure.
Fig. 3 is Ba4MGa4Se10Cl2Middle sample 1#～6#X ray diffracting spectrum.
Fig. 4 is Ba4MGa4Se10Cl2Middle sample 1#～4#Crystal FT-IR spectrum.
Fig. 5 is Ba4MGa4Se10Cl2Middle sample 1#～4#Crystal powder frequency multiplication intensity reference withAgGaS2(34 – 46 μ graph of a relation m).
Fig. 6 is Ba4MGa4Se10Cl2Middle sample 1#～4#Fluorescence spectrum.
Detailed description of the invention
Below in conjunction with embodiment, further set forth the application. Should be understood that these embodiment are only for sayingBright the application and be not used in restriction the application scope. Do not do in the situation of specified otherwise the application instituteUse raw material, all buy by commercial sources, directly use without specially treated.
The preparation of embodiment 1 sample
By BaCl2, barium metal powder, metal M, gallium powder and selenium powder mix all according to a certain percentageEven, obtain raw material; Raw material is put into graphite crucible; The graphite crucible that raw material is housed is placed in to quartzIn reaction tube, vacuum is evacuated to 10-2Pa also uses oxyhydrogen flame scorification sealing crystal reaction tube. Quartz is anti-Should put into the tube furnace with temperature controller by pipe, be heated to solid melting temperatur, and keep a period of time. SoAfter be cooled to after 300 DEG C to be no more than the speed program of 5 DEG C/h, stop heating, naturally cool toRoom temperature obtains described non-linear optical crystal material.
Sample number into spectrum, raw material proportioning, solid melting temperatur and retention time are as shown in table 1.
Table 1
The structural characterization of embodiment 2 samples
Sample 1#～6#X – ray single crystal diffraction on MercuryCCD type single crystal diffractometer, carry out,Mo target, K α radiation source (λ=0.07107nm), probe temperature 293K. And pass through Shelxtl97To carrying out structure elucidation. The crystallographic data result of each sample is as shown in table 2, crystal structure signalFigure as shown in Figure 1.
Table 2 sample 1#～6#Crystallographic data
Can find out sample 1#～6#There is identical crystal structure, structure is mainly by symmetrical T1The three dimensional network structure that the super tetrahedron of tetrahedron and T2 is alternately interconnected to form by sharing Se,Ba2+And Cl-Be filled among the cavity of three-dimensional grid. Wherein T1 is MSe4 6-Tetrahedron, T2 isBy four GaSe4 5-Super tetrahedron [the Ga that tetrahedron forms4Se10]8-。
Sample 1#～6#X – ray powder diffraction material phase analysis (XRD) in Rigaku companyOn MiniFlexII type X-ray diffractometer, carry out Cu target, K α radiation source (λ=0.154184nm).Sample 1#～6#The XRD spectra that obtains of powder X-ray RD figure and single crystal diffraction data fitting as Fig. 3 instituteShow. As seen from Figure 3, sample 1#～6#XRD figure and single crystal diffraction data fitting obtainXRD spectra is consistent, illustrates that gained sample has very high degree of crystallinity and purity.
The optical property of embodiment 3 samples characterizes
Sample 1#～6#Optical property at NicoletMagna750FT-IR infrared spectrometer and PELambda900 UV, visible light (near-infrared) absorb or the spectrometer that diffuses on characterize, result is as table 3Shown in.
Sample 1#～4#Light transmission as shown in Figure 4, frequency doubling property as shown in Figure 5, fluorescence propertyAs shown in Figure 6.
Can find out, utilize that the collaborative substitution technique of effective double ion that the application provides obtains 1#～6#Sample, has realized the function Composite of material. For example, Ba4Cu0.5Ga4.5Se10Cl2Compound is realizedSecond nonlinear (under 2.05 μ m laser excitations, 39 times that its powder frequency doubling intensity is AGS)With T1-T2 skeleton emission wavelength from ruddiness region (Ba3CsGa5Se10Cl2The emission wavelength of compound is711nm) extend near infrared region (Ba4Cu0.5Ga4.5Se10Cl2Emission wavelength be 880nm)Compound. Ba4MnGa4Se10Cl2Compound has been realized second nonlinear (in 2.05 μ m laser excitationsUnder, its powder frequency doubling intensity is AGS 30 times), red emission (Ba4MnGa4Se10Cl2Send outPenetrate wavelength Xem=700nm) and the function of magnetic compound.
Table 3 sample 1#～6#Optical performance data
*Reference and AgGaS2(m), laser wavelength of incidence is 2050nm to 30～46 μ.
The above, be only several embodiment of the application, not the application done to any type of limitSystem, although the application discloses as above with preferred embodiment, but be not in order to limit the application, anyThose skilled in the art, not departing from the scope of present techniques scheme, utilize above-mentioned taking offThe technology contents showing is made a little variation or is modified and is all equal to equivalent case study on implementation, all belongs to technologyWithin the scope of scheme.
Claims (10)
1. a non-linear optical crystal material, is characterized in that, has molecular formula as follows:
Ba4MGa4Se10Cl2
Wherein, M is metallic element, is selected from IIB family metallic element, VIIB family metallic element, VIIIAt least one in family's metallic element or M are by least one and IIIA family gold in IB family metallic elementBelong at least one composition in element; The crystal structure of described nonlinear crystalline material belongs to tetragonalSystem, space group is
2. non-linear optical crystal material according to claim 1, is characterized in that, described IIBFamily's metallic element is Zn, Cd; Described VIIB group metallic element is Mn; Metal unit of described VIII familyElement is Fe, Co; Described IB family metallic element is Cu; Described IIIA family metallic element is Ga.
3. non-linear optical crystal material according to claim 1, is characterized in that, structure cell ginsengNumber isα＝β＝γ＝90°。
4. non-linear optical crystal material according to claim 1, is characterized in that, structure cell ginsengNumber isα＝β＝γ＝90°。
5. non-linear optical crystal material according to claim 1, is characterized in that, described crystalline substanceThe molecular formula of body material is selected from Ba4ZnGa4Se10Cl2、Ba4CdGa4Se10Cl2、Ba4MnGa4Se10Cl2、Ba4Cu0.5Ga4.5Se10Cl2In at least one.
6. the method for preparing non-linear optical crystal material described in claim 1, is characterized in that, willContain BaCl2, barium metal, metal M, gallium and simple substance selenium raw material, pass through high temperature solid-state methodPrepare described non-linear optical crystal material; BaCl in described raw material2, barium metal, metal M,The molar ratio of gallium and simple substance selenium is BaCl2: barium metal: metal M: gallium: simple substanceSelenium=1:3:1:4:10.
7. method according to claim 6, is characterized in that, described high temperature solid-state method is by formerMaterial is placed at 870～1100 DEG C, keeps being no less than 50 hours.
8. method according to claim 6, is characterized in that, described high temperature solid-state method is by formerMaterial is placed at 870～1100 DEG C, keeps being no less than 100 hours; Then to be no more than the speed of 5 DEG C/hAfter degree programmed cooling to 300 DEG C, be cooled to room temperature, obtain described non-linear optical crystal material.
9. an Infrared Detectors in, is characterized in that, contains described in claim 1 to 5 any oneNon-linear optical crystal material and/or claim 6 to 8 any one described in method prepare non-Linear optical crystal material.
10. a middle infrared laser, is characterized in that, contains claim 1 to 5 any one instituteDescribed in the non-linear optical crystal material of stating and/or claim 6 to 8 any one, method preparesNon-linear optical crystal material.
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| CN107021462A (en) * | 2017-04-25 | 2017-08-08 | 中国工程物理研究院化工材料研究所 | Selenium gallium zinc barium compound, selenium gallium zinc barium infrared nonlinear optical crystal and its production and use |
| CN107399722A (en) * | 2017-08-15 | 2017-11-28 | 中国科学院新疆理化技术研究所 | Selenium silicon silver barium and selenium silicon silver barium mid and far infrared nonlinear optical crystal and preparation method and purposes |
| CN114232100A (en) * | 2021-10-01 | 2022-03-25 | 中国科学院福建物质结构研究所 | Inorganic compound crystal, preparation method thereof and application of inorganic compound crystal as nonlinear optical crystal |
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