CN105603531B - A kind of middle infrared nonlinear optical crystal, its preparation method and application - Google Patents
A kind of middle infrared nonlinear optical crystal, its preparation method and application Download PDFInfo
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- CN105603531B CN105603531B CN201410658470.7A CN201410658470A CN105603531B CN 105603531 B CN105603531 B CN 105603531B CN 201410658470 A CN201410658470 A CN 201410658470A CN 105603531 B CN105603531 B CN 105603531B
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Abstract
This application discloses a kind of nonlinear crystalline material, its preparation method and application responded with strong infrared frequency multiplication.Its nonlinear crystalline material has molecular formula as follows：Ba4MGa4Se10Cl2Wherein, M is metallic element, is made up of selected from least one of Group IIB metal element, VIIB races metallic element, group VIII metal element or M at least one of at least one of IB races metallic element and Group IIIA metallic element；The crystal belongs to tetragonal crystal system, and space group isThe powder frequency doubling intensity of material can reach commercial material AgGaS259 times, available for photoelectronic warfare, resource detection, space be anti-ballistic and communication etc..
Description
Technical field
The application is related to the multifunctional material and its system of FTIR radiation transmittance Complex Function during a kind of energy is realized
Preparation Method, belong to Inorganic Nonlinear Optical Materials field.
Background technology
Nonlinear optical crystal is the crystal that secondary above nonlinear optical effect is shown for laser highfield.It has
The nonlinear optical effects such as laser freuqency doubling, difference frequency, many times frequency multiplication, parametric oscillation and amplification, laser technology, military affairs and it is civilian on
More and more important effect is played.
According to its transmission region scope, nonlinear optical crystal can be divided into ultraviolet, visible and infrared light district three major types.Its
In, some ultraviolet and visual field crystal (such as KH2PO4(KDP),KTiOPO4(KTP),β-BaB2O4(BBO),LiB3O5(LBO))
All there is excellent optical property and be widely used in practice.
Existing infrared non-linear commercial material (such as ZnGeP2, AgGaS2, LiGaS2, LiInS2) damage from laser all be present
The low grade of threshold value each the defects of, it is impossible to meet growing practical application request.And middle infrared band (2-20 μm) is long-range
The important wave band of communication, middle infrared nonlinear optical crystal have important application in optoelectronic areas, such as shaken by optical parameter
Swing or the laser of near infrared band can be extended to middle infrared by the means such as optically erasing；The important laser of centering infrared light district
Frequency multiplication is carried out, so as to obtain laser of wavelength continuously adjustabe etc..So middle infrared non-linear optics (NLO) material is in photoelectricity pair
Anti-, resource detection, space are anti-ballistic, communication etc. has important application.
Therefore the new middle infrared nonlinear optical crystal material for finding or exploring synthesis premium properties is current non-linear
One of the difficult point of optical material research field and focus.And the Complex Function of middle infrared nonlinear optical crystal is even more one few
There is the frontier of developing.
The application passes through the T1-T2 three-dimensional anion frame compounds Ba to having reported for work3CsGa5Se10Cl2
(J.Am.Chem.Soc., 2012,134,2227-2235) implements effective double ion collaboration substitution, have successfully been obtained with strong
Infrared frequency multiplication response a kind of noval chemical compound Ba4MGa4Se10Cl2(M=Zn, Cd, Mn, Cu/Ga).Keeping crystalline framework knot
On the basis of structure is constant, the tetrahedral metal centers of T1, compound Ba are replaced with different transition metal4MGa4Se10Cl2Realize
Function and service.This effective double ion collaboration substitution strategy is the design synthesis of the multifunctional composite of functional direction
And performance regulation and control provide new thinking and direction.
The content of the invention
According to the one side of the application, there is provided a kind of nonlinear crystalline material responded with strong infrared frequency multiplication, should
Nonlinear crystalline material not only has excellent Nonlinear Second order Optical Properties, also with photoluminescent property, its powder frequency doubling intensity
It can reach commercial material AgGaS230~59 times.
The nonlinear crystalline material is characterised by thering is molecular formula as follows：
Ba4MGa4Se10Cl2
Wherein, M is metallic element, in Group IIB metal element, VIIB races metallic element, group VIII metal element
At least one or M is made up of at least one of at least one of IB races metallic element and Group IIIA metallic element；It is described non-
The crystal structure of linear crystal material belongs to tetragonal crystal system, and space group is
Preferably, the Group IIB metal element is Zn, Cd.
Preferably, the VIIB groups metallic element is Mn.
Preferably, the group VIII metal element is Fe, Co.
Preferably, IB races metallic element is Cu.
Preferably, the Group IIIA metallic element is Ga.
Preferably, the cell parameter of the non-linear optical crystal material is α=β
=γ=90 °.
Preferably, the cell parameter of the non-linear optical crystal material isα=β=
γ=90 °.
Preferably, the molecular formula of the crystalline material is selected from Ba4ZnGa4Se10Cl2、Ba4CdGa4Se10Cl2、
Ba4MnGa4Se10Cl2、Ba4Cu0.5Ga4.5Se10Cl2、Ba4FeGa4Se10Cl2、Ba4CoGa4Se10Cl2At least one of.
Preferably, the molecular formula of the crystalline material is selected from Ba4ZnGa4Se10Cl2、Ba4CdGa4Se10Cl2、
Ba4MnGa4Se10Cl2、Ba4Cu0.5Ga4.5Se10Cl2At least one of.Wherein, Ba4Cu0.5Ga4.5Se10Cl2It can also be expressed as
Ba4Cu0.5Ga0.5Ga4Se10Cl2。
The crystal structure of the nonlinear crystalline material as shown in figure 1, its structure mainly by symmetrical T1 tetrahedrons and
The three dimensional network structure that the super tetrahedrons of T2 are alternately interconnected to form by sharing Se, Ba2+And Cl-It is filled in the sky of three-dimensional grid
Among chamber.Wherein T1 is MSe4 6-Tetrahedron, T2 are by four GaSe4 5-Tetrahedroid into super tetrahedron [Ga4Se10]8-。
The nonlinear crystalline material is except with excellent Nonlinear Second order Optical Properties, also with photoluminescent property.Example
Such as, compound Ba4Cu0.5Ga4.5Se10Cl2Under 2.05 μm of laser excitation, its powder frequency doubling intensity is AgGaS2(it can be abbreviated as
AGS) 39 times.Ba4Cu0.5Ga4.5Se10Cl2Launch wavelength (λem=880nm) with the compound phase ratio of isomorphism from visible red
Light region extends near infrared region.It is expected that it is visited in laser frequency conversion, Electro-optical Modulation, Preset grating information processing, near-infrared
The high-tech areas such as pin (can be used for bio-imaging) have significant application value.
According to the another aspect of the application, there is provided the preparation method of the non-linear optical crystal material, it is characterised in that
BaCl will be contained2, barium metal, metal M, the raw material of gallium and elemental selenium be placed under vacuum condition, using high temperature solid-state legal system
It is standby to obtain the non-linear optical crystal material.
Preferably, BaCl in the raw material2, barium metal, metal M, the molar ratio of gallium and elemental selenium be BaCl2:Gold
Belong to barium:Metal M:Gallium:Elemental selenium=1:3:1:4:10.
Preferably, the high temperature solid-state method keeps being no less than 50 hours for raw material is placed at 870~1100 DEG C.
Preferably, the high temperature solid-state method keeps being no less than 100 hours for raw material is placed at 870~1100 DEG C；Then
After being cooled to 300 DEG C with the speed program no more than 5 DEG C/h, room temperature is cooled to, obtains the nonlinear optical crystal material
Material.
According to a kind of preferred embodiment, the preparation method of the non-linear optical crystal material, it is characterised in that extremely
Contain less and have the following steps：
(a) by BaCl2, barium metal, metal M, gallium and elemental selenium according to molar ratio be BaCl2:Barium metal:Metal
M:Gallium:Elemental selenium=1:3:1:4:10 ratio is well mixed, and obtains raw material；
(b) raw material obtained by step (a) is placed in container, sealed after being vacuumized container；
(c) closed container equipped with raw material is placed in heater, is warming up to 870~1100 DEG C, holding at least 100 is small
Shi Hou, after being cooled to 300 DEG C with the speed program no more than 5 DEG C/h stop heating, naturally cool to room temperature produce it is described non-
Linear optical crystal material.
The principle of the preparation method is the T1-T2 three-dimensional anion frame compounds by having reported for work applicant
Ba3CsGa5Se10Cl2Implement effective double ion collaboration substitution, refer to Fig. 2.Utilize this effective double ion collaboration substitution plan
Slightly, the BaCl of stoichiometric proportion is passed through2It is blended in simple substance Ba, M, Ga, Se under the conditions of high temperature process heat and obtains target product.
The introducing of new metallic element, realize the Composite of crystalline material function.For example, herein described nonlinear crystal
Ba in material4Cu0.5Ga4.5Se10Cl2Second nonlinear is realized to expand to closely from red light region with T1-T2 skeletons emission wavelength
Region of ultra-red it is compound；Ba4MnGa4Se10Cl2Realize the function and service of second nonlinear, red emission and magnetic.
According to the another aspect of the application, there is provided a kind of middle infrared detector, it is characterised in that containing any of the above-described non-thread
The non-linear optical crystal material that property optical crystal material and/or any of the above-described method are prepared.
According to the another aspect of the application, there is provided a kind of mid-infrared laser device, it is characterised in that containing any of the above-described non-thread
The non-linear optical crystal material that property optical crystal material and/or any of the above-described method are prepared.
The application has the advantages that：
(1) this application provides a kind of new middle infrared nonlinear optical crystal, the nonlinear crystalline material not only to have
Excellent Nonlinear Second order Optical Properties, also it can reach commercial material AgGaS with photoluminescent property, its powder frequency doubling intensity2's
59 times.
(2) this application provides the method for preparing above-mentioned middle infrared nonlinear optical crystal material.Using it is effective double from
Son collaboration substitution, crystalline material of the synthesis with complex function.
(3) nonlinear crystalline material provided herein has excellent Nonlinear Second order Optical Properties, in can be used for
Infrared detector and laser.
Brief description of the drawings
Fig. 1 is Ba4MGa4Se10Cl2Crystal structure schematic diagram.
Fig. 2 is Ba3CsGa5Se10Cl2Double ion collaboration substitution generation Ba4MGa4Se10Cl2Schematic diagram.
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 and AgGaS2(34-46 μm)
Graph of a relation.
Fig. 6 is Ba4MGa4Se10Cl2Middle sample 1#~4#Fluorescence spectrum.
Embodiment
With reference to embodiment, the application is expanded on further.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.In the case of not doing specified otherwise, raw material used in this application, purchased by commercial sources
Buy, it is not specially treated directly to use.
The preparation of the sample of embodiment 1
By BaCl2, barium metal powder, metal M, gallium powder and selenium powder be well mixed according to a certain percentage, obtain raw material；Will
Raw material is put into graphite crucible；Graphite crucible equipped with raw material is placed in crystal reaction tube, vacuum is evacuated to 10-2Pa simultaneously uses hydrogen-oxygen
Flame scorification seals crystal reaction tube.Crystal reaction tube is put into the tube furnace with temperature controller, is heated to solid melting temperatur, and
Kept for a period of time.Then after being cooled to 300 DEG C with the speed program no more than 5 DEG C/h, stop heating, naturally cool to
Room temperature produces the 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 the sample of embodiment 2
Sample 1#~6#X-ray single crystal diffraction carried out on Mercury CCD type single crystal diffractometers, Mo targets, K α radiation
Source (λ=0.07107nm), test temperature 293K.And by Shelxtl97 to carrying out structure elucidation.The crystallography of each sample
Data result is as shown in table 2, and crystal structure schematic diagram is as shown in Figure 1.
The sample 1 of table 2#~6#Crystallographic data
As can be seen that sample 1#~6#There is identical crystal structure, structure is mainly surpassed by symmetrical T1 tetrahedrons and T2
The three dimensional network structure that tetrahedron is alternately interconnected to form by sharing Se, Ba2+And Cl-Be filled in three-dimensional grid cavity it
In.Wherein T1 is MSe4 6-Tetrahedron, T2 are by four GaSe4 5-Tetrahedroid into super tetrahedron [Ga4Se10]8-。
Sample 1#~6#X-ray powder diffraction material phase analysis (XRD) penetrated in the MiniFlex II types X of Rigaku companies
Carried out on line diffractometer, Cu targets, K α radiation source (λ=0.154184nm).Sample 1#~6#Powder xrd pattern and single crystal diffraction number
The XRD spectra obtained according to fitting is as shown in Figure 3.As seen from Figure 3, sample 1#~6#XRD and single crystal diffraction data be fitted
Obtained XRD spectra is consistent, illustrates that gained sample has very high crystallinity and purity.
The optical property of the sample of embodiment 3 characterizes
Sample 1#~6#Optical property it is purple in Nicolet Magna 750FT-IR infrared spectrometers and PE Lambda900
Outer visible (near-infrared) absorbs or diffused spectrometer upper table sign, as a result as shown in table 3.
Sample 1#~4#Light transmission as shown in figure 4, frequency doubling property as shown in figure 5, fluorescence property is as shown in Figure 6.
As can be seen that the effective double ion provided using the application cooperates with 1 that substitution technique obtains#~6#Sample, realize
The function and service of material.For example, Ba4Cu0.5Ga4.5Se10Cl2Compound realizes second nonlinear (in 2.05 μm of laser
Excite down, its powder frequency doubling intensity is 39 times of AGS) with T1-T2 skeletons emission wavelength from red light region (Ba3CsGa5Se10Cl2
The launch wavelength of compound is 711nm) extend near infrared region (Ba4Cu0.5Ga4.5Se10Cl2Launch wavelength be 880nm)
It is compound.Ba4MnGa4Se10Cl2Compound realize second nonlinear (under 2.05 μm of laser excitation, its powder frequency doubling intensity
For 30 times of AGS), red emission (Ba4MnGa4Se10Cl2Emission wavelength lambdaem=700nm) and magnetic function and service.
The sample 1 of table 3#~6#Optical performance data
*Reference and AgGaS2(30~46 μm), laser wavelength of incidence 2050nm.
It is described above, only it is several embodiments of the application, any type of limitation is not done to the application, although this Shen
Please with preferred embodiment disclose as above, but and be not used to limit the application, any person skilled in the art, do 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 scheme.
Claims (8)
1. a kind of non-linear optical crystal material, it is characterised in that there is molecular formula as follows：
Ba4MGa4Se10Cl2
Wherein, M is metallic element；The crystal structure of the nonlinear crystalline material belongs to tetragonal crystal system, and space group is
The non-linear optical crystal material is double ion collaboration substitution；
The molecular formula of the crystalline material is selected from Ba4ZnGa4Se10Cl2、Ba4CdGa4Se10Cl2、Ba4MnGa4Se10Cl2、
Ba4Cu0.5Ga4.5Se10Cl2、Ba4FeGa4Se10Cl2、Ba4CoGa4Se10Cl2At least one of.
2. non-linear optical crystal material according to claim 1, it is characterised in that cell parameter isα=β=γ=90 °.
3. non-linear optical crystal material according to claim 1, it is characterised in that cell parameter isα=β=γ=90 °.
4. prepare the method for non-linear optical crystal material described in claim 1, it is characterised in that BaCl will be contained2, barium metal,
Metal M, gallium and elemental selenium raw material, the non-linear optical crystal material is prepared by high temperature solid-state method；It is described
BaCl in raw material2, barium metal, metal M, the molar ratio of gallium and elemental selenium be BaCl2:Barium metal:Metal M:Gallium:
Elemental selenium=1:3:1:4:10.
5. according to the method for claim 4, it is characterised in that the high temperature solid-state method is that raw material is placed in into 870~1100
At DEG C, keep being no less than 50 hours.
6. according to the method for claim 4, it is characterised in that the high temperature solid-state method is that raw material is placed in into 870~1100
At DEG C, keep being no less than 100 hours；Then after being cooled to 300 DEG C with the speed program no more than 5 DEG C/h, it is cooled to room
Temperature, obtain the non-linear optical crystal material.
7. a kind of middle infrared detector, it is characterised in that contain the nonlinear optical crystal described in any one of claims 1 to 3
The non-linear optical crystal material that any one of material and/or claim 4 to 6 methods described are prepared.
8. a kind of mid-infrared laser device, it is characterised in that contain the nonlinear optical crystal described in any one of claims 1 to 3
The non-linear optical crystal material that any one of material and/or claim 4 to 6 methods described are prepared.
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| CN107399722B (en) * | 2017-08-15 | 2019-05-14 | 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 |
| CN114232100B (en) * | 2021-10-01 | 2022-12-06 | 中国科学院福建物质结构研究所 | Preparation method of inorganic nonlinear optical crystal containing transition metal |
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| CN101033558A (en) * | 2006-03-08 | 2007-09-12 | 中国科学院福建物质结构研究所 | Infrared window material |
| CN101935880A (en) * | 2009-06-30 | 2011-01-05 | 陈文通 | Novel chalcogenide semiconductor material |
| CN101935881A (en) * | 2009-06-30 | 2011-01-05 | 陈文通 | Novel IIB-VIA-VIIA compound semiconductor material |
| CN102409407A (en) * | 2011-11-09 | 2012-04-11 | 中国科学院福建物质结构研究所 | Infrared non-linear optical material Ba3AGa5Se10Cl2 and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033558A (en) * | 2006-03-08 | 2007-09-12 | 中国科学院福建物质结构研究所 | Infrared window material |
| CN101935880A (en) * | 2009-06-30 | 2011-01-05 | 陈文通 | Novel chalcogenide semiconductor material |
| CN101935881A (en) * | 2009-06-30 | 2011-01-05 | 陈文通 | Novel IIB-VIA-VIIA compound semiconductor material |
| CN102409407A (en) * | 2011-11-09 | 2012-04-11 | 中国科学院福建物质结构研究所 | Infrared non-linear optical material Ba3AGa5Se10Cl2 and preparation method thereof |
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