CN110607556A - Crystal material, preparation and growth method thereof and application of crystal material in nonlinear optics - Google Patents
Crystal material, preparation and growth method thereof and application of crystal material in nonlinear optics Download PDFInfo
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
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Abstract
The application discloses a crystal material, a preparation and growth method thereof and application thereof in nonlinear optics. The crystalline material has Na2MSn2Se6Wherein M represents Zn and/or Cd. The crystal material is synthesized by a medium-temperature polysulfide flux method. The crystal material has excellent infrared nonlinear optical performance, and the frequency doubling signal intensity is commercial AgGaS when phase matching is realized22.2-3 times of the laser damage threshold, 5-10 times of the laser damage threshold, and has potential application value in the field of middle and far infrared nonlinear optics.
Description
Technical Field
The crystal material belongs to the field of nonlinear optical materials, and particularly relates to preparation, growth and application of an infrared nonlinear optical crystal.
Background
The nonlinear optical (NLO) material can realize the frequency conversion effect on laser and has irreplaceable effect in a laser system. The laser covering two atmospheric window wave bands (3-5 and 8-14 mu m) can be realized through the middle and far infrared NLO crystal, and the laser has important research prospects in the fields of remote sensing detection, environmental monitoring, space safety and the like. KH exists in the ultraviolet-visible light region2PO4(KDP),KTiOPO4(KTP),β-BaB2O4(BBO) and the like, but because these oxides have vibration absorption in the infrared band, the application of these oxides in the infrared region is greatly limited.
The materials currently used in the middle and far infrared region are mainly chalcogenide AgGaS2，AgGaSe2And phosphide ZnGeP2. Although the materials have high transmittance in middle and far infrared bands and large effective frequency multiplication coefficient, the materials have the defects of low laser damage threshold or serious two-photon absorption and the like, and the application of the materials in high-power devices is restricted. Therefore, exploring and synthesizing the medium and far infrared NLO crystal material which has large nonlinear coefficient, high laser damage threshold, phase matching capability and good mechanical and chemical stability has become one of the difficulties and the leading edge direction in the nonlinear optical material research field.
Disclosure of Invention
According to one aspect of the present application, a crystalline material is provided that has both a high doubling factor and a high laser damage threshold.
The crystalline material is characterized by having a chemical formula shown in formula I;
Na2MSn2Se6formula I
Wherein M represents Zn and/or Cd.
Optionally, the crystal structure of the crystalline material belongs to the monoclinic system, Fdd2 non-centrosymmetric space group;
the crystal material has unit cell parameters of α＝β＝γ＝90°，Z＝8。
Optionally, the crystalline material has a chemical formula of Na2ZnSn2Se6Cell parameter ofα＝β＝γ＝90°，Z＝8。
Optionally, the crystalline material has a chemical formula of Na2CdSn2Se6Cell parameter ofα＝β＝γ＝90°，Z＝8。
Optionally, the size of the crystal material is 0.02-0.5 mm.
Optionally, the size of the crystal material is 0.5-5 mm.
Optionally, when phase matching is carried out under 1910nm laser, the frequency doubling intensity of the crystal material is AgGaS22.2-3 times of the total weight of the powder.
Optionally, the threshold value of laser damage of the crystalline material at 1064nm is AgGaS25 to 10 times of the total weight of the composition.
Optionally, the optical transmittance range of the crystal material is 0.6-25 μm.
In one embodiment, the crystalline material has the chemical formula Na2ZnSn2Se6Cell parameter ofα＝β＝γ＝90°，Z＝8。
In one embodiment, the crystalline material has the chemical formula Na2ZnSn2Se6Cell parameter ofα＝β＝γ＝90°，Z＝8。
In one embodiment, the crystalline material has the chemical formula Na2CdSn2Se6Cell parameter ofα＝β＝γ＝90°，Z＝8。
In one embodiment, the crystalline material has the chemical formula Na2CdSn2Se6Cell parameter ofα＝β＝γ＝90°，Z＝8。
The crystal structure is shown in figure 1 and is [ MSn2Se6]n(M ═ Zn/Cd) three-dimensional framework, Na+Ions are inserted into the slits of the pore channel. All Sn and Zn/Cd atoms coordinate with four Se atoms to form SnSe4And (Zn/Cd) Se4A tetrahedron. Wherein SnSe4The tetrahedrons are connected by common vertex angles and are respectively along [011 ]]Anddirection forming one dimension SnSe3]nAnd (3) a chain. Two-direction adjacency [ SnSe3]nChain through (Zn/Cd) Se4Tetrahedrally connected and form [ MSn ]2Se6]nA three-dimensional network.
As another aspect of the present application, there is provided a method of preparing any of the crystalline materials described above. The method is convenient to operate, and the crystal material is easy to crystallize, so that the method is suitable for industrial production.
The method for preparing the crystal material is characterized by adopting an intermediate-temperature polysulfide flux method, and at least comprises the following steps:
mixing raw materials containing a sodium source, a tin source, a selenium source and an M source, placing the mixture under a vacuum condition, heating the mixture to 450-600 ℃, preserving the heat for not less than 72 hours, cooling the mixture to 150-300 ℃ at the speed of 1-5 ℃/h, and then cooling the mixture to room temperature to obtain the crystal material.
Optionally, the resulting crystalline material is larger in size by increasing the incubation time and/or decreasing the cooling rate.
Optionally, the molar ratio of the sodium source, the tin source, the selenium source and the zinc/cadmium M element source in the raw material is:
Na：M：Sn：Se＝2：1～1.5：2～3：6～7；
wherein the moles of the sodium source are based on the moles of sodium element contained in the sodium source; the number of moles of the M source is calculated by the number of moles of the M element contained in the M source; the mole number of the tin source is calculated by the mole number of tin element contained in the tin source; the mole number of the selenium source is calculated by the mole number of selenium element contained in the selenium source.
Optionally, in the raw material, the sodium source is selected from sodium simple substance and Na2At least one of Se;
the tin source is selected from Sn simple substance and SnSe2At least one of;
the selenium source is selected from Se simple substance and Na2At least one of Se;
the M source is selected from at least one of Zn elementary substance and Cd elementary substance.
Optionally, in the raw material, the sodium source is Na2Se, wherein the Sn source is Sn simple substance, and the Se source is Se simple substance and Na2Se and M source is a Zn elementary substance and/or a Cd elementary substance;
the molar ratio of the sodium source, the tin source, the selenium source and the zinc/cadmium M element source in the raw materials is as follows:
Na2Se：M：Sn：Se＝1：1～1.5：2～3：5～6。
alternatively, Na2Se：M：Sn：Se＝1：1：2.1：6。
Optionally, in the raw material, the sodium source, the tin source, the selenium source and the M source are all Na2MSn2Se6A phase pure compound.
Alternatively, the Na2MSn2Se6Adding a certain amount of sodium selenide and selenium into the pure-phase compound to be used as polysulfide fluxing agent, wherein the molar ratio of the sodium selenide to the selenium is 1: 5 to 7.
Optionally, the method comprises the steps of:
mixing raw materials containing a sodium source, a tin source, a selenium source and an M source in a graphite crucible, then putting the graphite crucible into a quartz tube, and vacuumizing to a vacuum condition.
Optionally, the vacuum condition is a pressure not higher than 1 × 10-4Torr。
As an embodiment, the method comprises the following steps:
mixing raw materials containing a sodium source, a tin source, a selenium source and an M source, placing the mixture under a vacuum condition, heating the mixture to 380-420 ℃ at a speed of 30-35 ℃/h, preserving heat for 4-6 hours, heating the mixture to 450-650 ℃ at a speed of 15-25 ℃/h, preserving heat for 72-85 hours, cooling the mixture to 380-420 ℃ at a speed of 2-4 ℃/h, cooling the mixture to 200-270 ℃ at a speed of 4-5 ℃/h, and cooling the mixture to room temperature to obtain the crystal material; or
Mixing raw materials containing a sodium source, a tin source, a selenium source and an M source, placing the mixture under a vacuum condition, heating the mixture to 450-650 ℃ at a speed of 15-18 ℃/h, preserving the heat for 95-97 hours, cooling the mixture to 380-420 ℃ at a speed of 0.5-1 ℃/h, cooling the mixture to 180-220 ℃ at a speed of 1-3 ℃/h, cooling the mixture to 100-120 ℃ at a speed of 3-5 ℃/h, and cooling the mixture to room temperature to obtain the crystal material; or
Will contain Na2MSn2Se6Mixing raw materials of pure-phase compounds, placing the mixture in a vacuum condition, heating the mixture to 580-650 ℃ at a speed of 15-18 ℃/h, preserving the heat for 95-97 hours, cooling the mixture to 380-420 ℃ at a speed of 0.5-1 ℃/h, cooling the mixture to 180-220 ℃ at a speed of 1-3 ℃/h, cooling the mixture to 100-120 ℃ at a speed of 3-5 ℃/h, and cooling the mixture to room temperature to obtain the crystal material.
Preferably, the crystalline material is washed with DMF and/or ethanol and dried to obtain a pure phase.
As an implementation mode, the raw materials or the compounds are put into a graphite crucible after being ground uniformly in a pure phase mode, are packaged in a large-caliber quartz tube in a vacuum mode, are heated to 600 ℃, are kept warm for more than 72 hours, are cooled to 400 ℃ at a cooling rate of less than 1 ℃/h, and are cooled to room temperature to obtain large-size crystals.
Optionally, a certain amount of sodium selenide and selenium are added into the graphite crucible as polysulfide fluxing agent, wherein the molar ratio of the sodium selenide to the selenium is 1: 5 to 7.
According to still another aspect of the present application, there is provided an infrared nonlinear optical crystal material, characterized by containing the crystal material or the crystal material prepared according to the method.
According to another aspect of the present application, there is provided a nonlinear optical device comprising the infrared nonlinear optical crystal.
Optionally, the nonlinear optical device is used for frequency doubling generation, sum frequency, difference frequency, optical parametric amplification and optical parametric oscillation.
As an embodiment, the present application provides Na2MSn2Se6The crystal is applied as an infrared nonlinear optical crystal material. Commercial AgGaS is used for realizing frequency multiplication signal intensity when phase matching is realized under 1910nm laser22.2-3 times of that of the laser, and the laser damage threshold value of 1064nm is AgGaS25-10 times of the optical power, and has potential application value in the field of middle and far infrared nonlinear optics. Can be used for preparing nonlinear optical devices with the use wave band of 0.6-25 μm, and is applied to frequency doubling generation, sum frequency, difference frequency, optical parametric amplification and optical parametric oscillation.
In the present application, the term "middle-temperature polysulfide flux method" sulfur means sulfur, selenium or tellurium as chalcogen, and the amount is excessive, and middle temperature means the crystal growth holding temperature is between 200 ℃ and 700 ℃.
The beneficial effects that this application can produce include:
(1) the present application provides a novel crystalline material. The crystal material has excellent infrared nonlinear optical performance, and when phase matching is realized under 1910nm laser, the frequency multiplication signal intensity is commercial AgGaS22.2-3 times of that of the laser, and the laser damage threshold value of 1064nm is AgGaS25-10 times of the total weight of the powder.
(2) The application provides a preparation method of the crystal material, which is prepared by using a medium-temperature polysulfide flux method. The method has simple steps, simple chemical composition and high repeatability, and is suitable for the requirement of batch production.
(3) The application provides a method for growing the crystal material. The large-size quartz tube containing the graphite crucible can protect a crystal material growth instrument, and the graphite wall is favorable for heterogeneous nucleation and is suitable for crystal growth of a compound synthesized by a polysulfide flux method.
(4) The nonlinear optical crystal material provided by the application is a crystal with excellent infrared nonlinear optical effect, has a wide optical light transmission range of 0.6-25 mu m, is easy to crystallize, has good mechanical, chemical and thermal stability, can be used for preparing a nonlinear optical device with a use wave band of 0.6-25 mu m, is applied to frequency doubling generation, sum frequency, difference frequency, optical parametric amplification and optical parametric oscillation, and has important application value.
Drawings
FIG. 1 is a schematic structural diagram of two infrared nonlinear optical crystal materials.
Figure 2 is an experimental and theoretical fit powder XRD diffractogram of sample # 1.
Figure 3 is an experimental and theoretical fit powder XRD diffractogram of sample # 4.
FIG. 4 shows samples 1# and 4# and a standard sample AgGaS under a 1910nm laser2The variation curve of the frequency doubling signal with the particle size.
Fig. 5 is a photograph of sample # 1.
Fig. 6 is a photograph of sample 4 #.
Fig. 7 is a photograph of sample # 5.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
EXAMPLE 1 preparation of Crystal sample
Sample # 1 (Na)2ZnSn2Se6) Synthesis of crystals
Starting material Na2Se, Zn, Sn and Se powder are mixed in a molar ratio of 1: 1: 2.1: 6, 300mg in total, weighed in a glove box and mixed wellThen, the crucible was placed in a graphite crucible, and the graphite crucible was placed in a quartz tube having an inner diameter of about 11 mm. The quartz tube was evacuated to a pressure of about 1x10 using a vacuum system-4After the Torr, the quartz tube was sealed by melting with an oxyhydrogen flame. Putting the sealed quartz tube into a muffle furnace capable of controlling temperature in an inclined way, and heating to medium temperature for synthesis. The temperature curve is that the mixture is heated from room temperature to 400 ℃ in 12 hours and is kept at 400 ℃ for 5 hours; heating to 600 ℃ within 10 hours, and keeping the temperature for 84 hours; then cooling to 400 ℃ at the speed of 3 ℃/h, then cooling to 250 ℃ at the speed of 5 ℃/h, closing the temperature control instrument, and naturally cooling to room temperature. Opening the synthesized quartz tube in a fume hood, taking out a sample in the graphite crucible, washing with DMF (dimethyl formamide) and drying with ethanol, and manually picking out the pure phase of the red microcrystal of the compound through a microscope to obtain Na2ZnSn2Se6Crystal, denoted sample # 1.
Synthesis of large-size sample 2# crystal by medium-temperature polysulfide flux method
Weighing 3g of the total raw material, Na2Se, M, Sn and Se in molar ratio Na2Se: m: sn: se is 1: 1.2: 2.1: 5.5, mixing, grinding uniformly, putting into a flat-bottom graphite crucible with the inner diameter of 20mm, vacuumizing and packaging in a large-caliber bottle-shaped quartz tube with the lower inner diameter of 25mm, the outer diameter of 30mm and the upper inner diameter of 11 mm. Putting the sealed quartz tube into a muffle furnace capable of controlling temperature in an inclined way, and heating to medium temperature for synthesis. Heating from room temperature to 600 deg.C in 36 hr, maintaining for 96 hr, cooling to 400 deg.C at 1 deg.C/h rate, cooling to 200 deg.C at 2 deg.C/h rate, cooling to 100 deg.C at 4 deg.C/h rate, closing the temperature controller, and naturally cooling to room temperature. The synthesized quartz tube was opened in a fume hood, and the sample in the graphite crucible was taken out, whereby millimeter-sized sample 2# crystals could be obtained.
Synthesis of large-size sample 3# crystal by using medium-temperature polysulfide flux method
Weighing 3g of sample No. 1 pure phase, uniformly grinding, placing into a flat-bottom graphite crucible with the inner diameter of 20mm, vacuumizing and packaging in a large-caliber bottle-shaped quartz tube with the lower inner diameter of 25mm, the outer diameter of 30mm and the upper inner diameter of 11 mm. Putting the sealed quartz tube into a muffle furnace capable of controlling temperature in an inclined way, and heating to medium temperature for synthesis. Heating from room temperature to 600 deg.C in 36 hr, maintaining for 96 hr, cooling to 400 deg.C at 1 deg.C/h rate, cooling to 200 deg.C at 2 deg.C/h rate, cooling to 100 deg.C at 4 deg.C/h rate, closing the temperature controller, and naturally cooling to room temperature. The synthesized quartz tube was opened in a fume hood, and the sample in the graphite crucible was taken out, whereby a millimeter-sized sample 3# crystal was obtained.
Sample # 4 (Na)2CdSn2Se6) Synthesis of crystals
Starting material Na2Se, Cd, Sn and Se powders in a weight ratio of 1: 1: 2.1: 6, 300mg in total, was weighed in a glove box and mixed well, and then placed in a graphite crucible, which was then placed in a quartz tube having an inner diameter of about 11 mm. The quartz tube was evacuated to a pressure of about 1x10 using a vacuum system-4After the Torr, the quartz tube was sealed by melting with an oxyhydrogen flame. Putting the sealed quartz tube into a muffle furnace capable of controlling temperature in an inclined way, and heating to medium temperature for synthesis. The temperature curve is that the mixture is heated from room temperature to 400 ℃ in 12 hours and is kept at 400 ℃ for 5 hours; heating to 600 ℃ within 10 hours, and keeping the temperature for 84 hours; then cooling to 400 ℃ at the speed of 3 ℃/h, then cooling to 250 ℃ at the speed of 5 ℃/h, closing the temperature control instrument, and naturally cooling to room temperature. Opening the synthesized quartz tube in a fume hood, taking out a sample in the graphite crucible, washing with DMF (dimethyl formamide) and drying with ethanol, and manually picking out the pure phase of the red microcrystal of the compound through a microscope to obtain Na2CdSn2Se6Crystal, sample # 4.
Sample # 5 Large Scale (Na)2ZnSn2Se6) Growth of crystals
Weighing 3g of sample No. 1 pure phase in total, and adding 0.5g of sodium selenide and selenium in total, wherein the molar ratio of the sodium selenide to the selenium is 1: and 6, after grinding uniformly, putting the ground material into a flat-bottom graphite crucible with the inner diameter of 20mm, and then vacuumizing and packaging the flat-bottom graphite crucible in a large-caliber bottle-shaped quartz tube with the lower inner diameter of 25mm, the outer diameter of 30mm and the upper inner diameter of 11 mm. Putting the sealed quartz tube into a muffle furnace capable of controlling temperature in an inclined way, and heating to medium temperature for synthesis. Heating from room temperature to 600 deg.C in 36 hr, maintaining for 96 hr, cooling to 400 deg.C at 1 deg.C/h rate, cooling to 200 deg.C at 2 deg.C/h rate, cooling to 100 deg.C at 4 deg.C/h rate, closing the temperature controller, and naturally cooling to room temperature. The synthesized quartz tube was opened in a fume hood, and the sample in the graphite crucible was taken out, whereby large-sized sample # 5 crystals could be obtained.
Table 1 list of crystal sizes for example 1
| Sample numbering | Morphology of the sample | Description of the dimensions |
| 1# | Red flaky and blocky crystals | 0.02-2mm |
| 2# | Red flaky and blocky crystals | 0.2-2mm |
| 3# | Red flaky and blocky crystals | 0.2-5mm |
| 4# | Red flaky and blocky crystals | 0.02-3mm |
| 5# | Red flaky and blocky crystals | 0.2-5mm |
The samples in the table are a batch of samples prepared by the method of example 1 and having the dimensions in the ranges shown in table 1. For example, 1#Is sample No. 1 (Na) of example 12ZnSn2Se6) The synthesis of crystals yielded a batch of samples with a size ranging between 0.02 and 2 mm.
Example 2 structural characterization of the samples
The X-ray powder diffraction phase analysis and the single crystal X-ray diffraction test were carried out on sample # 1 to sample # 5. X-ray powder diffraction phase analysis (PXRD) data were collected using a Rigaku MiniFlex600 powder diffractometer and illuminated using a Cu-Kalpha target reflection patternThe test temperature is 293K, the 2 theta angle range is 5-65 degrees, the scanning step width is 0.02 degree, the current is 100mA, and the voltage is 30 KV. Single Crystal X-ray diffraction test data were collected at 293K using a Rigaku Pilatus CCD Single Crystal diffractometer and X-ray emission using a Mo-K α target equipped with a graphite monochromatorIntensity data were collected using the omega scanning technique and data were reduced using the Rigaku crystalispro software.
Performing structure analysis on the obtained crystal material:
sample 1#Sample 2#Sample 3#Sample No. 5#Has unit cell parameters of α＝β＝γ＝90°，Z＝8，Sample No. 4#Has unit cell parameters ofα＝β＝γ＝90°，Z＝8，
Na2ZnSn2Se6And Na2CdSn2Se6Is a heterogeneous isomorphic compound, which belongs to the monoclinic Fdd2 noncentrosymmetric space group. The crystal structure is shown in figure 1, wherein M represents Zn and/or Cd.
Sample 1#The coordinates of each atom are shown in table 2:
TABLE 2
| Atom | x | y | z |
| Sn(1) | 0.6391(2) | 0.3754(2) | 0.5234(4) |
| Se(1) | 0.5140(2) | 0.6490(3) | 0.6856(6) |
| Se(2) | 0.5796(2) | 0.4679(3) | 0.3142(6) |
| Se(3) | 0.6130(2) | 0.1964(3) | 0.5877(6) |
| Zn(1) | 0.5000 | 0.5000 | 0.5031(10) |
| Na(1) | 0.6413(2) | 0.8323(2) | 0.5159(4) |
The atomic coordinates of sample # 2, sample # 3 and sample # 5 are similar to sample # 1.
Sample No. 4#The atomic coordinates are shown in table 3:
TABLE 3
| Atom | x | y | z |
| Sn(1) | 0.6413(2) | 0.3839(4) | 0.6003(7) |
| Cd(1) | 0.5000 | 0.5000 | 0.5782(13) |
| Se(1) | 0.5846(3) | 0.4712(7) | 0.3831(10) |
| Se(2) | 0.7364(3) | 0.4096(7) | 0.5225(13) |
| Se(3) | 0.6156(4) | 0.2045(6) | 0.6603(12) |
| Na(1) | 0.6989(19) | 0.5844(4) | 0.3393(6) |
Sample 1#And 4#The comparison of the experimental powder XRD diffraction pattern and the fitting XRD diffraction pattern obtained by the single crystal is respectively shown in figures 2 and 3, the two XRD derivative patterns are highly consistent, and the obtained compound crystal material is proved to have high purity and crystallinity.
The powder XRD diffractograms of sample # 2, sample # 3 and sample # 5 were similar to sample # 1.
EXAMPLE 3 frequency doubling Performance testing of samples
Mixing the microcrystalline sample with AgGaS2Samples of 30-50,50-100, 150, 200, 250 μm in total five particle sizes were sieved through a sieve and measured using a modified Kurtz-Perry method using an infrared laser with a wavelength of 1910nm emitted from an OPOTEK VibrantaOPO laser. The output frequency multiplication signal is recorded by using a Charge Coupled Detector (CCD) and is compared with a reference AgGaS2And comparing the signal peak intensity at the frequency doubling wavelength (955nm) to obtain the relative frequency doubling coefficient of the sample. And (4) carrying out phase matching capability test through the relationship of particle size and frequency doubling signals.
As shown in FIG. 4, the frequency doubling signals for both compounds increased with increasing particle size, indicating sample 1#And 4#Has phase matching capability at 1910 nm. Comparison of the frequency doubling signal intensity of the sample with a particle size of 200-#And 4#Respectively show the same grain size AgGaS2About 3.0 and 2.2 times higher.
The frequency doubling performance of sample # 2, sample # 3 and sample # 5 was similar to sample # 1.
Example 4 laser Damage threshold test of samples
And irradiating the sample by using 1064nm laser of a Yd-YAG laser, and testing the laser damage threshold size of the sample by using an R-on-1 method. The reference sample is AgGaS2The particle diameter is 50-100 μm, and the pulse width is taup10ns and a repetition frequency of 1 Hz. And gradually increasing the power of the laser until the color of the sample changes, and recording the laser power at the moment as the damage threshold of the sample. The test results are shown in Table 4, sample 1#And 4#The laser damage threshold values of (a) are 15.29 and 30.28MW/cm2This is AgGaS respectively2Laser damage threshold (3.06 MW/cm)2) 5 and 10 times higher.
The laser damage thresholds of sample # 2, sample # 3 and sample # 5 are similar to sample # 1.
TABLE 4 Na2ZnSn2Se6，Na2CdSn2Se6And a standard sample AgGaS2Laser damage threshold of
Although the present application has been described with reference to a preferred embodiment, it should not be construed as limited to the embodiment set forth herein, but rather should be construed broadly within its scope as defined in the claims.
Claims (10)
1. A crystalline material having a formula shown in formula I;
Na2MSn2Se6formula I
Wherein M represents Zn and/or Cd.
2. The crystalline material of claim 1, wherein the crystalline structure of the crystalline material belongs to the monoclinic system, Fdd2 noncentrosymmetric space group;
the crystal material has unit cell parameters of α＝β＝γ＝90°，Z＝8。
3. The crystalline material of claim 1, wherein the crystalline material has a chemical formula of Na2ZnSn2Se6Cell parameter of α ═ β ═ γ ═ 90 °, Z ═ 8; or
The chemical formula of the crystal material is Na2CdSn2Se6Cell parameter of α＝β＝γ＝90°，Z＝8。
4. The crystalline material of claim 1, wherein the crystalline material has a size of 0.02 to 0.5 mm;
preferably, the size of the crystal material is 0.5-5 mm;
preferably, when phase matching is carried out under 1910nm laser, the frequency doubling intensity of the crystal material is AgGaS22.2-3 times of the total weight of the powder;
preferably, the threshold value of laser damage of the crystal material at 1064nm is AgGaS25-10 times of the total weight of the composition;
preferably, the optical light transmission range of the crystal material is 0.6-25 μm.
5. A method for preparing a crystalline material as claimed in any one of claims 1 to 4, characterized in that a medium-temperature polysulfide flux method is used, comprising at least the following steps:
mixing raw materials containing a sodium source, a tin source, a selenium source and an M source, placing the mixture under a vacuum condition, heating the mixture to 450-600 ℃, preserving the heat for not less than 72 hours, cooling the mixture to 150-300 ℃ at the speed of 1-5 ℃/h, and then cooling the mixture to room temperature to obtain the crystal material.
6. The method according to claim 5, characterized in that the molar ratio of the sodium source, the tin source, the selenium source and the M element source in the raw material is:
Na：M：Sn：Se＝2：1～1.5：2～3：6～7；
wherein the moles of the sodium source are based on the moles of sodium element contained in the sodium source; the number of moles of the M source is calculated by the number of moles of the M element contained in the M source; the mole number of the tin source is calculated by the mole number of tin element contained in the tin source; the mole number of the selenium source is calculated by the mole number of selenium element contained in the selenium source;
preferably, in the raw material, the sodium source is selected from sodium simple substance and Na2At least one of Se;
the tin source is selected from Sn simple substance and SnSe2At least one of;
the selenium source is selected from Se simple substance and Na2At least one of Se;
the M source is selected from at least one of Zn elementary substance and Cd elementary substance;
more preferably, in the raw material, the sodium source is Na2Se, wherein the Sn source is Sn simple substance, and the Se source is Se simple substance and Na2Se and M source is a Zn elementary substance and/or a Cd elementary substance;
the molar ratio of the sodium source, the tin source, the selenium source and the zinc/cadmium M element source in the raw materials is as follows:
Na2Se：M：Sn：Se＝1：1～1.5：2～3：5～6；
more preferably, in the raw material, the sodium source, the tin source, the selenium source and the M source are all Na2MSn2Se6A phase-pure compound;
even more preferably, the Na2MSn2Se6Adding a certain amount of sodium selenide and selenium into the pure-phase compound to be used as polysulfide fluxing agent, wherein the molar ratio of the sodium selenide to the selenium is 1: 5 to 7.
7. The method of claim 5,
mixing raw materials containing a sodium source, a tin source, a selenium source and an M source in a graphite crucible, then putting the graphite crucible into a quartz tube, and vacuumizing to a vacuum condition;
preferably, the vacuum condition is a pressure of not higher than 1 × 10-4Torr。
8. The method of claim 5, comprising the steps of:
mixing raw materials containing a sodium source, a tin source, a selenium source and an M source, placing the mixture under a vacuum condition, heating the mixture to 380-420 ℃ at a speed of 30-35 ℃/h, preserving heat for 4-6 hours, heating the mixture to 450-650 ℃ at a speed of 15-25 ℃/h, preserving heat for 72-85 hours, cooling the mixture to 380-420 ℃ at a speed of 2-4 ℃/h, cooling the mixture to 200-270 ℃ at a speed of 4-5 ℃/h, and cooling the mixture to room temperature to obtain the crystal material; or
Mixing raw materials containing a sodium source, a tin source, a selenium source and an M source, placing the mixture under a vacuum condition, heating the mixture to 450-650 ℃ at a speed of 15-18 ℃/h, preserving the heat for 95-97 hours, cooling the mixture to 380-420 ℃ at a speed of 0.5-1 ℃/h, cooling the mixture to 180-220 ℃ at a speed of 1-3 ℃/h, cooling the mixture to 100-120 ℃ at a speed of 3-5 ℃/h, and cooling the mixture to room temperature to obtain the crystal material; or
Will contain Na2MSn2Se6Mixing raw materials of pure-phase compounds, placing the mixture in a vacuum condition, heating the mixture to 580-650 ℃ at a speed of 15-18 ℃/h, preserving the heat for 95-97 hours, cooling the mixture to 380-420 ℃ at a speed of 0.5-1 ℃/h, cooling the mixture to 180-220 ℃ at a speed of 1-3 ℃/h, cooling the mixture to 100-120 ℃ at a speed of 3-5 ℃/h, and cooling the mixture to room temperature to obtain the crystal material.
9. An infrared nonlinear optical crystal material comprising the crystal material according to any one of claims 1 to 4 or the crystal material produced by the method according to any one of claims 5 to 8.
10. A nonlinear optical device comprising the infrared nonlinear optical crystal according to claim 9;
preferably, the nonlinear optical device is used for frequency doubling generation, sum frequency, difference frequency, optical parametric amplification and optical parametric oscillation.
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