CN109402740A - A kind of crystalline material, preparation method and the nonlinear optical crystal comprising it - Google Patents
A kind of crystalline material, preparation method and the nonlinear optical crystal comprising it Download PDFInfo
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- CN109402740A CN109402740A CN201811624256.4A CN201811624256A CN109402740A CN 109402740 A CN109402740 A CN 109402740A CN 201811624256 A CN201811624256 A CN 201811624256A CN 109402740 A CN109402740 A CN 109402740A
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- 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
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- 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
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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Abstract
This application discloses a kind of crystalline material, preparation method, the non-linear optical crystal material comprising it and its applications in the laser.The crystalline material chemical formula is [AM3Q5]n；A represents at least one of Na, K, Rb, Cs；M represents Ga and/or In；Q represents S and/or Se；1≤n≤4.The crystalline material has excellent infrared non-linear optical property, and frequency multiplication intensity is up to one-size commercialization AgGaS27.0 times, laser damage threshold is up to commercialization AgGaS211 times of (AGS can be abbreviated as).In terms of the frequency conversion devices such as mid and far infrared wave band of laser frequency multiplication and frequency, difference frequency, optical parametric oscillation, there is important application value.
Description
The application is divisional application, female case are as follows: a kind of crystalline material, preparation method and the non-linear optical crystal comprising it
Body, application No. is 201611108475.8, applying date 2016-12-06.
Technical field
This application involves a kind of crystalline material, preparation method, include its nonlinear optical crystal and in the laser
Using belonging to nonlinear optical material field.
Background technique
Mid and far infrared nonlinear optical material is widely used in laser freuqency doubling, optical parametric oscillation and sound, electro-optical device etc..In recent years
Come, with the rapid development of the technologies such as CO2 laser radar detection, laser communications, infrared telemetry, infrared navigation, to high quality, height
The requirement of performance FTIR radiation transmittance is more more and more urgent.
Currently, the generation of solid-state mid and far infrared wave band of laser is mainly based upon nonlinear optics principle and infrared non-linear light
Learn crystal converter technique.The material of existing mid and far infrared wave band application mainly has AgGaS2, AgGaSe2And ZnGeP2Deng these
Material has all played a key effect in high-tech area and military equipment, but these crystal are also deposited in comprehensive performance at present
In defect.In recent years, more excellent performance of infrared non-linear crystal material is needed with desired raising with the development of technology
Material, therefore explore synthesis while there is the non-linear crystalline substance of novel mid and far infrared of big nonlinear factor and high laser damage threshold
Body material becomes the important research direction of infrared nonlinear material.
Summary of the invention
According to the one aspect of the application, a kind of novel crystalline material is provided, which has excellent infrared
Non-linear optical property, frequency multiplication intensity is up to one-size commercialization AgGaS27.0 times, laser damage threshold is up to commercialization AgGaS2
11 times of (AGS can be abbreviated as).In the frequency conversion devices side such as mid and far infrared wave band of laser frequency multiplication and frequency, difference frequency, optical parametric oscillation
Face has important application value.
The crystalline material, which is characterized in that there is the chemical formula as shown in Formulas I or Formula II:
[A2M4Q7]nFormulas I
[AM3Q5]nFormula II
In Formulas I and Formula II, A represents at least one of Na, K, Rb, Cs；M represents Ga and/or In；Q represents S and/or Se；
1≤n≤4。
As the technical solution of the application, the structure of the crystalline material with chemical formula shown in formula I belongs to
Rhombic system；The structure of its crystalline material is as shown in Figure 1, in the compound of Formula I comprising 4 A atoms (in Na, K, Rb, Cs
At least one, i.e. Na/K/Rb/Cs occupies identical crystallography position；With Na be to exemplify in Fig. 1), 8 M atoms (Ga and/
Or In, i.e. Ga/In occupy identical crystallography position；With In it is to exemplify in Fig. 1) and 14 Q atoms (S and/or Se, i.e.,
S/Se occupies identical crystallography position), wherein 8 Q atoms are that part occupies, occupation rate 25-30%, other atoms are complete
It occupies.The three-dimensional structure of Formula I is made of along c-axis direction by sharing Se/S connection two kinds of one-dimensional super tetrahedron chain
It forms, then forms the three-dimensional structure that zigzag connects, A along the direction a with b+Ion is filled in the duct of its formation.Two kind one
Tieing up chain is respectively∞ 1(M4Q11)10-Super tetrahedron chain and∞ 1(M4Q12)12-Super tetrahedron chain.
As the technical solution of the application, the structure of the crystalline material with the chemical formula as shown in Formula II belongs to
Trigonal system；The structure of its crystalline material as shown in Fig. 2, chemical formula be in the compound of II comprising 2 A atoms (Na, K, Rb,
At least one of Cs, i.e. Na/K/Rb/Cs occupy identical crystallography position；In Fig. 2 with Na be exemplify), 6 M atoms
(S and/or Se, i.e. S/Se occupy identical for (Ga and/or In, i.e. Ga/In occupy identical crystallography position) and 10 Q atoms
Crystallography position；In Fig. 2 with Se be exemplify).Its three-dimensional structure is by one-dimensional [M6Q10]2-Chain and the A being filled in duct
Atomic building.One-dimensional [M6Q10]2-Chain is by MQ4Tetrahedron is accumulated along the direction c.
Preferably, it is the crystalline material of Formulas I -1, the crystal material that chemical formula is Formula II -1 that the crystalline material, which is chemical formula,
One of material, crystalline material that chemical formula is Formula II -2；
Na2In4SSe6Formulas I -1
Chemical formula is the crystalline material of Formulas I -1, belongs to the Pca2 of rhombic system1Space group, cell parameter areα=90 °, β=90 °, γ=
90, Z=4；
NaGaIn2Se5Formula II -1
Chemical formula is the crystalline material of Formula II -1, belongs to the R32 space group of trigonal system, cell parameter isα=90 °, β=90 °, γ
=120, Z=6；
NaIn3Se5Formula II -2
Chemical formula is the crystalline material of Formula II -2, belongs to the P3 of trigonal system2Space group, cell parameter areα=90 °, β=90 °, γ
=120, Z=6.
According to the another aspect of the application, the method for preparing any of the above-described crystalline material is provided, which is characterized in that at least wrap
Containing following steps: the raw material containing element representated by element representated by element representated by A, M and Q is placed in vacuum condition
It is lower that the crystalline material is prepared using high temperature solid-state method.
Those skilled in the art can require selection high temperature solid-state method former when preparing above-mentioned crystalline material according to actual production
The ratio of each component in material.
As the embodiment of the application, the crystalline material is the crystalline material that chemical formula is Formulas I, the raw material
The molar ratio of element representated by middle A, element representated by element and Q representated by M are as follows:
A:M:Q=2:4:7~15.
As the embodiment of the application, the crystalline material is the crystalline material that chemical formula is Formula II, the original
The molar ratio of element representated by A, element representated by element and Q representated by M in material are as follows:
A:M:Q=1:3:5~10.
Preferably, the raw material is by A2Q, M simple substance and Q simple substance are mixed to get.
Preferably, the high temperature solid-state method is that raw material is placed under vacuum condition, is heated to 600 DEG C~950 DEG C and keeps not
After 48 hours, cooling down is up to the crystalline material.It is further preferred that the high temperature solid-state method is to be placed in raw material
Under vacuum condition, after being heated to 700 DEG C~950 DEG C holdings 48 hours~96 hours, cooling down is up to the crystalline material.More
It is further preferred that the cooling down is after being first down to 200 DEG C~400 DEG C with the rate of temperature fall of 1~5 DEG C/h, to turn off and add
Heat is cooled to room temperature.
According to the another aspect of the application, a kind of non-linear optical crystal material is provided, which is characterized in that contain above-mentioned
At least one of one crystalline material, the crystalline material being prepared according to any of the above-described method.Preferably, the nonlinear optical
Crystalline material is learned by least one of any of the above-described crystalline material, the crystalline material being prepared according to any of the above-described method group
At.
According to the another aspect of the application, the application of above-mentioned non-linear optical crystal material in the laser is provided.
The beneficial effect that the application can generate includes but is not limited to:
(1) this application provides a kind of novel crystalline materials.The crystalline material has outstanding infrared non-linear optics
Performance.Its nonlinear effect of measuring may be up to commercialization AgGaS27.0 times；Its laser damage threshold may be up to commercialization
AgGaS211 times.
(2) this application provides the preparation methods of above-mentioned crystalline material, and the crystal material is prepared with high temperature solid-state method
Material.The method step is simple, purity is high, better crystallinity degree, the high income of gained crystalline material, is suitble to large-scale industry metaplasia
It produces.
(3) non-linear optical crystal material provided herein is a kind of polarity that infrared non-linear optical effect is excellent
Crystal, it is contemplated that in terms of the frequency conversion devices such as mid and far infrared wave band of laser frequency multiplication and frequency, difference frequency, optical parametric oscillation, have important
Application value.
Detailed description of the invention
Fig. 1 is the structural schematic diagram with the crystalline material of chemical formula shown in formula I.
Fig. 2 is the structural schematic diagram of the crystalline material with the chemical formula as shown in Formula II.
Fig. 3 is sample I-1#The experimental powder X-ray diffraction data measured and the crystal obtained according to mono-crystalline structures parsing
Learn the calculated powder X-ray diffraction data that data are fitted.
Fig. 4 is sample II-1#The experimental powder X-ray diffraction data measured and the crystalline substance obtained according to mono-crystalline structures parsing
The calculated powder X-ray diffraction data that body data are fitted.
Fig. 5 is sample II-2#The experimental powder X-ray diffraction data measured and the crystalline substance obtained according to mono-crystalline structures parsing
The calculated powder X-ray diffraction data that body data are fitted.
Fig. 6 is different-grain diameter range sample 1-1#, sample 2-1#, sample 2-2#Frequency multiplication test result and AgGaS2Pair
Than.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
The preparation of 1 sample of embodiment
Sample I-1#Preparation
By Na2S (23.2mg), In (136.3mg) and Se (140.5mg) ingredient and after mixing are packed into graphite crucible,
It is put into quartz ampoule, is evacuated to 10-4Torr (1 support=133.322 pas) tube sealing, is put into Muffle furnace and is slowly heated to 850 DEG C,
After heat preservation 72 hours, after 3 DEG C/h is cooled to 300 DEG C, turn off Muffle furnace cooled to room temperature, obtaining chemical formula is
Na2In4SSe6Red crystals, be denoted as sample I-1#。
Sample I-2#~sample I-5#Preparation
Specific preparation process is the same as sample I-1#, the difference is that proportion scale, high temperature solid state reaction temperature, high temperature solid-state
Reaction time, rate of temperature fall；The number of gained sample and the relationship of above-mentioned condition and chemical formula are as shown in table 1.
1 sample I-2 of table#~sample I-6#Preparation
Sample II-1#Preparation
By Na2Se (26.1mg), Ga (29.2mg), In (96.1mg) and Se (149.0mg) ingredient and after mixing, dress
Enter graphite crucible, be put into quartz ampoule, is evacuated to 10-4Torr tube sealing is put into Muffle furnace and is slowly heated to 850 DEG C, heat preservation
After 72 hours, after 3 DEG C/h is cooled to 300 DEG C, turn off Muffle furnace cooled to room temperature, obtaining chemical formula is
NaGaIn2Se5Yellow crystals, be denoted as sample II-1#。
Sample II-2#Preparation
By Na2Se (24.6mg), In (136.0mg) and Se (139.0mg) ingredient and after mixing are packed into graphite earthenware
Crucible is put into quartz ampoule, is evacuated to 10-4Torr tube sealing is put into Muffle furnace after being slowly heated to 950 DEG C, heat preservation 96 hours,
After 3 DEG C/h is cooled to 300 DEG C, turn off Muffle furnace cooled to room temperature, obtaining chemical formula is NaIn3Se5Red it is brilliant
Body is denoted as sample II-2#。
Sample II-3#~sample II-6#Preparation
Specific preparation process is the same as sample II-1#, the difference is that proportion scale, high temperature solid state reaction temperature, high temperature are solid
Phase reaction time, rate of temperature fall；The number of gained sample and the relationship of above-mentioned condition and chemical formula are as shown in table 2.
2 sample II-3 of table#~sample II-6#Preparation
The structural characterization of 2 sample of embodiment
Sample I-1#~I-6#X-ray powder diffraction material phase analysis (XRD) Rigaku company MiniFlex II type
It is carried out on X-ray diffractometer, Cu target, K α radiation source (λ=0.154184nm).The result shows that sample I-1#~I-6#It is high-purity
Degree and high-crystallinity sample, crystal structure types are identical, and the peak position of principal character peak is identical, each peak peak intensity with element A,
M element, the difference of Q element are slightly changed.
Sample I-1#X-ray single crystal diffraction carried out on Rigaku Pilatus type single crystal diffractometer, Mo target, K α spoke
Penetrate source (λ=0.07107nm), test temperature 293K.And pass through 97 pairs of progress structure elucidations of Shelxtl, parsing result are as follows:
Chemical formula is Na2In4SSe6, belong to the Pca2 of rhombic system1Space group, cell parameter are α=90 °, β=
90 °, γ=90, Z=4.
Na2In4SSe6Structure cell in, include 4 Na atoms, 8 In atoms and 14 Se/S atoms, wherein 8 Se
Identical crystallography position is occupied by S portion, occupation rate is 25~30%, other atoms are to occupy entirely.The three-dimensional knot of Formula I
Structure is made of along c-axis direction two kinds of one-dimensional super tetrahedron chain and is formed by connecting by sharing Se/S, then along the direction a and b
Form the three-dimensional structure of zigzag connection, Na+Ion is filled in the duct of its formation.Two kinds of one-dimensional chains are respectively∞ 1[In4(Se/
S)11]10-Super tetrahedron chain and∞ 1[In4(Se/S)12]12-Super tetrahedron chain.
Sample I-1#The XRD diffraction theory map being fitted by single crystal data and the XRD diffraction pattern that test obtains in fact
Spectrum compares fig. 3, it is shown that the XRD that the XRD diffracting spectrum being fitted by single crystal data is obtained with test in fact spreads out
It is consistent to penetrate map height, it was demonstrated that gained sample is the sample of high-purity and high-crystallinity.
In conjunction with sample I-1#Single crystal data and sample I-1#~I-6#X-ray powder diffraction data, sample I-1#
~I-6#Crystal structure schematic diagram it is as shown in Figure 1.
Sample II-1#~II-6#X-ray powder diffraction material phase analysis (XRD) Rigaku company MiniFlex II
It is carried out on type X-ray diffractometer, Cu target, K α radiation source (λ=0.154184nm).The result shows that sample II-1#~II-6#It is
The sample of high-purity and high-crystallinity, crystal structure types are identical, and the peak position of principal character peak is identical, and each peak peak intensity is with A
Element, M element, the difference of Q element are slightly changed.
Sample II-1#With sample II-2#X-ray single crystal diffraction it is enterprising in Rigaku Pilatus type single crystal diffractometer
Row, Mo target, K α radiation source (λ=0.07107nm), test temperature 293K.And by Shelxtl97 to progress structure elucidation.
Sample II-1#Parsing result are as follows:
Chemical formula is NaGaIn2Se5, belong to the R32 space group of trigonal system, cell parameter is α=90 °, β=90 °,
γ=120, Z=6.
NaGaIn2Se5Structure cell in, comprising 2 Na atoms, 2 Ga atoms and 4 In atoms, (Ga and In occupy identical
Crystallography position) and 10 Se atoms.Its three-dimensional structure is by one-dimensional [Ga2In4Se10]2-Chain and the Na being filled in duct
Atomic building.One-dimensional [Ga2In4Se10]2-Chain is by (Ga/In) Se4Tetrahedron is accumulated along the direction c.
Sample II-2#Parsing result are as follows:
Chemical formula is NaIn3Se5, belong to the P3 of trigonal system2Space group, cell parameter are α=90 °, β=
90 °, γ=120, Z=6.
Sample II-1#With sample II-2#The XRD diffraction theory map being fitted by single crystal data is obtained with test in fact
XRD diffracting spectrum compare it is as shown in Figure 4 and Figure 5 respectively, it can be seen that the XRD diffraction pattern being fitted by single crystal data
It composes consistent with the XRD diffracting spectrum height that test in fact obtains, it was demonstrated that gained sample is the sample of high-purity and high-crystallinity.
In conjunction with sample II-1#With sample II-2#Single crystal data and sample II-1#~II-6#X-ray powder diffraction
Data, sample II-1#~II-6#Crystal structure schematic diagram it is as shown in Figure 2.
The frequency multiplication of 3 sample of embodiment is tested
Respectively to sample I-1#~I-6#, sample II-1#~II-6#Carry out frequency multiplication test, the specific steps are as follows:
The wavelength for using OPO technology to generate is the laser of 1910nm as fundamental frequency light, irradiates tested crystal powder, benefit
The intensity that generated 955nm second harmonic is detected with charge coupled cell (CCD), by sample to be tested and standard sample AgGaS2
It grinds respectively, and sifts out the crystal of different-grain diameter with standard screen, granularity is respectively 30-50 μm, and 50-75 μm, 75-100 μm,
100-125 μm, 125-150 μm and 150-200 μm.Frequency-doubled signal is observed with the variation tendency of granularity, judges whether it can be with
Realize phase matched, under conditions of same, the intensity and reference crystal AgGaS of second harmonic caused by comparative sample2
Generated second harmonic intensity, to obtain the relative size of sample frequency-doubled effect.Wherein, with sample I-1#, sample II-1#
With sample II-2#For Typical Representative, result is as shown in Figure 6.
As seen from Figure 6,75~100 μm of partial size of sample, sample I-1#, sample II-1#With sample II-2#Powder
Frequency-doubled signal is AgGaS respectively27.0 times, 2.1 times and 0.3 times.Sample I-2#~I-6#Powder frequency doubling signal be commercialization
AgGaS22~7 times between；Sample II-3#~II-6#Powder frequency doubling signal be commercial AgGaS20.5~5 between.
The laser damage threshold of 4 sample of embodiment is tested
Respectively to sample I-1#~I-6#, sample II-1#~II-6#Carry out laser damage threshold test, specific steps are such as
Under:
Using the wavelength for adjusting the Nd:YAG solid state laser of Q to generate is the laser of 1064nm as light source, and irradiation is tested
Crystal powder, sift out institute's sample and reference AgGaS with standard screen2The crystal of crystal different-grain diameter, granularity are 50-75 μ
m.It is gradually increased with laser intensity, the variation of observation institute's sample surface, until the blackening of sample surfaces color sample, judges it at this time
Laser intensity is laser damage threshold, under identical condition, comparative sample laser damage threshold and reference crystal AgGaS2Institute
The laser damage threshold of generation, to obtain the relative size of sample laser damage threshold.With sample I-1#, sample II-1#And sample
Product II-2#For Typical Representative, the results are shown in Table 3.
As can be seen from Table 3, sample I-1#, sample II-1#With sample II-2#Laser damage threshold be AgGaS respectively2
6,7 and 11 times.Sample I-2#~I-6#Laser damage threshold be commercial AgGaS25~9 between；Sample II-3#~
II-6#Laser damage threshold be commercial AgGaS26~11 between.
Table 3
The above is only several embodiments of the application, not does any type of limitation 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, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (10)
1. a kind of crystalline material, which is characterized in that have the chemical formula as shown in Formula II:
[AM3Q5]nFormula II
In Formula II, A represents at least one of Na, K, Rb, Cs；M represents Ga and/or In；Q represents S and/or Se；1≤n≤4.
2. crystalline material according to claim 1, which is characterized in that the crystal material with the chemical formula as shown in Formula II
The structure of material belongs to trigonal system.
3. crystalline material according to claim 1, which is characterized in that the crystalline material is the crystalline substance that chemical formula is Formula II -1
One of body material, crystalline material that chemical formula is Formula II -2；
NaGaIn2Se5Formula II -1
Chemical formula is the crystalline material of Formula II -1, belongs to the R32 space group of trigonal system, cell parameter isα=90 °, β=90 °, γ
=120 °, Z=6；
NaIn3Se5Formula II -2
Chemical formula is the crystalline material of Formula II -2, belongs to the P3 of trigonal system2Space group, cell parameter areα=90 °, β=90 °, γ
=120, Z=6.
4. the method for preparing any one of the claims 1 to 3 crystalline material, which is characterized in that include at least following steps: will
Raw material containing element representated by element representated by element representated by A, M and Q is placed under vacuum condition solid using high temperature
The crystalline material is prepared in phase method.
5. according to the method described in claim 4, it is characterized in that, the crystalline material is the crystal material that chemical formula is Formula II
Expect, the molar ratio of element representated by A, element representated by element and Q representated by M in the raw material are as follows:
A:M:Q=1:3:5~10.
6. according to the method described in claim 4, it is characterized in that, the raw material is by A2Q, M simple substance and Q simple substance are mixed to get.
7. according to the method described in claim 4, it is characterized in that, the high temperature solid-state method is that raw material is placed in vacuum condition
Under, it is heated to 600 DEG C~950 DEG C and keeps no less than after 48 hours, cooling down is up to the crystalline material；
Preferably, the high temperature solid-state method is that raw material is placed under vacuum condition, is heated to 700 DEG C~950 DEG C and is kept for 48 hours
After~96 hours, cooling down is up to the crystalline material.
8. the method according to the description of claim 7 is characterized in that the cooling down is the first rate of temperature fall with 1~5 DEG C/h
After being down to 200 DEG C~400 DEG C, turns off heating and be cooled to room temperature.
9. a kind of non-linear optical crystal material, which is characterized in that containing the described in any item crystalline materials of claims 1 to 3,
At least one of the crystalline material being prepared according to any one of claim 4 to 8 the method.
10. the application of non-linear optical crystal material described in claim 9 in the laser.
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| CN110284196B (en) * | 2019-07-24 | 2020-07-31 | 中国科学院福建物质结构研究所 | Lithium-containing crystal material and preparation method and application thereof |
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| CN109402740B (en) | 2020-06-26 |
| CN106757365B (en) | 2019-07-30 |
| CN106757365A (en) | 2017-05-31 |
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