CN110578173B - Nonlinear optical crystal strontium-lithium-silicon-sulfur and preparation method and application thereof - Google Patents
Nonlinear optical crystal strontium-lithium-silicon-sulfur and preparation method and application thereof Download PDFInfo
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- IDBJICZXPNGRFY-UHFFFAOYSA-N [S].[Si].[Li].[Sr] Chemical compound [S].[Si].[Li].[Sr] IDBJICZXPNGRFY-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910020358 SiS4 Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 5
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- JOHMULOEZGCUDU-UHFFFAOYSA-N [Si]=S.[Li].[Sr] Chemical compound [Si]=S.[Li].[Sr] JOHMULOEZGCUDU-UHFFFAOYSA-N 0.000 claims description 16
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- 238000001816 cooling Methods 0.000 claims description 12
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 4
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910013321 LiB3O5 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a nonlinear optical crystal strontium-lithium-silicon-sulfur, a preparation method and application thereof, wherein the chemical formula of the nonlinear optical crystal strontium-lithium-silicon-sulfur is SrLi2SiS4Molecular weight is 257.83, it is colorless transparent single crystal of non-central symmetrical structure, with [ LiS4]、[SiS4]And [ SrS ]8]The groups constitute structural motifs. The invention adopts a high-temperature solid-phase synthesis method to synthesize the nonlinear optical crystal strontium lithium silicon sulfur, has excellent optical performance, longer infrared absorption cut-off edge, wide band gap, high laser damage threshold and large nonlinear optical coefficient, and has wide potential application value as a novel intermediate and far infrared nonlinear optical crystal in a high-power infrared laser system.
Description
Technical Field
The invention relates to a middle and far infrared band laser frequency doubling crystal, in particular to a nonlinear optical crystal strontium lithium silicon sulfur and a preparation method and application thereof.
Background
With the advent of lasers, a series of novel optical phenomena was discovered in succession, of which nonlinear optical effects are one. In 1961, Franken (Franken) irradiated a beam of ruby laser on a quartz crystal, and the nonlinear optical frequency doubling effect was found for the first time, and then the research sequence of the nonlinear optical material was opened.
The nonlinear optical effect is caused by the interaction between laser and medium, when a laser beam with a certain polarization direction passes through a nonlinear optical crystal (such as AgGaS) in a certain incident direction2) The frequency of the beam will change. When laser light propagates in a medium with a non-zero second-order polarizability, nonlinear optical effects such as frequency doubling, sum frequency, difference frequency, optical parametric amplification and the like can be generated. Laser is a coherent monochromatic light source with high intensity and good directivity, and is widely applied to the fields of scientific research, industry, traffic, national defense, medical health and the like, however, due to the particularity of the laser generation mechanism, a practical laser medium cannot be found for each wavelength, so that various laser light sources which utilize nonlinear optical crystals for frequency conversion to obtain wide tuning become the leading topic of laser technology development.
Nonlinear optical crystal materials can be classified into three major categories according to the range of the transmission waveband: middle and far infrared nonlinear optical materials, visible light and near infrared band nonlinear optical materials and ultraviolet and deep ultraviolet band nonlinear optical materials. The major nonlinear optical materials at present mainly comprise KDP (KH)2PO4）、BBO（β-BaB2O4）、LBO（LiB3O5) And AGS (AgGaS)2) And the like. The output of the infrared light source, particularly the middle and far infrared light source, needs a pumping source with higher energy, the problem of crystal damage under high-power laser can be solved by improving the laser damage threshold, and the output power is greatly improved. Generally, the size of the bandgap of the crystal is an important factor in determining the laser damage threshold, and the larger the bandgap, the higher the laser damage threshold in general. Most of the infrared nonlinear optical materials in use today are ABC2Chalcopyrite of the type, e.g. AgGaS2And ZnGeP2And the like, but the crystals have some serious defects, such as a low laser damage threshold, a two-photon absorption problem to near-infrared laser (such as Nd: YAG 1064 nm), and difficulty in obtaining large-size and high-quality single crystals due to serious anisotropic thermal expansion, and the like, and therefore, how to prepare the mid-far infrared nonlinear optical crystals with a high laser damage threshold is one of the current research hotspots.
Disclosure of Invention
One object of the present invention is to provide a strontium lithium silicon sulfide compound.
The second purpose of the invention is to provide a preparation method of the strontium lithium silicon sulfur compound.
The invention also aims to provide a nonlinear optical crystal strontium lithium silicon sulfur.
The fourth purpose of the invention is to provide a preparation method of the nonlinear optical crystal strontium-lithium-silicon-sulfur.
The fifth purpose of the invention is to provide the application of the nonlinear optical crystal strontium-lithium-silicon-sulfur.
One of the objects of the invention is achieved by:
a strontium lithium silicon sulfur compound with the chemical formula of SrLi2SiS4Molecular weight is 257.83, which is a colorless transparent pure sample of strontium lithium silicon sulfide.
Furthermore, the strontium lithium silicon sulfur compound is a strontium lithium silicon sulfur crystal, is a non-centrosymmetric single crystal, belongs to a tetragonal crystal system, and has a space group ofI-42mUnit cell parameters are a = b = 6.469(3) Å, c = 7.689(7) Å = β = γ =90 °, Z = 2, unit cell volume V = 321.8(4) Å3。
Specifically, the valences of the Sr atom, the Li atom, the Si atom and the S atom in the strontium-lithium-silicon-sulfur crystal structure are respectively +2, +1, +4 and-2; li atom forms [ LiS ] with adjacent four S atoms4]A tetrahedral structure; the Si atom also forms [ SiS ] with its adjacent four S atoms4]A tetrahedron; [ LiS ]4]The tetrahedrons form a layered structure with a common vertex connection, with layers of [ SiS4]Tetrahedron connection forms a ring-shaped pore passage; the Sr atom is inlaid in [ LiS4]And [ SiS4]In the ring-shaped pore canal formed by tetrahedral link, 8 coordinated SrS is formed8]A dodecahedron.
Furthermore, the strontium lithium silicon sulfur crystal is a middle-far infrared nonlinear optical crystal, the band gap of the strontium lithium silicon sulfur crystal is 3.94 eV, the infrared cut-off edge is 20 mu m, and the laser damage threshold is about AgGaS221 times of the optical system, the nonlinear optical effect is strong: under the irradiation of 2.09 mu m fundamental frequency light, the frequency doubling capability of the crystal powder sample is commercial crystal AgGaS within the range of the granularity of 200-250 mu m2About 0.4 times of KH2PO4(KDP) 13 times higher.
The second purpose of the invention is realized by the following steps:
a preparation method of a strontium lithium silicon sulfur compound comprises the following steps:
(a) SrS and Li with the molar ratio of 1: 1-5: 12S and SiS2The raw materials are mixed evenly and put into a graphite crucible and then a quartz glass tube, and the vacuum degree is 10-5~10-1Vacuumizing under the condition of Pa, and then sealing;
(b) putting the sealed quartz glass tube in the step (a) into a high-temperature sintering furnace, heating to 400-700 ℃, and preserving heat for 7-15 h; then heating to 750-950 ℃, and preserving the heat for 70-110 h; and cooling to room temperature to obtain the strontium lithium silicon sulfur compound.
In the step (a), SrS and Li are weighed in an airtight container with water content and oxygen content of 0.01-0.2 ppm2S and SiS2Raw materials; preferably, the airtight container is a glove box filled with an inert gas, preferably argon.
In the step (b), preferably, the temperature is increased to 400-700 ℃ at the temperature increase rate of 20-40 ℃/h; preferably, the temperature is increased to 750-950 ℃ at the temperature increase rate of 25-40 ℃/h; preferably, cooling to room temperature at the rate of 2-7 ℃/h.
The third purpose of the invention is realized by the following steps:
a nonlinear optical crystal strontium lithium silicon sulfur with the chemical formula of SrLi2SiS4Molecular weight is 257.83, it is colorless transparent single crystal with non-central symmetrical structure, and space group isI-42mUnit cell parameters are a = b = 6.469(3) Å, c = 7.689(7) Å = β = γ =90 °, Z = 2, unit cell volume V = 321.8(4) Å3。
Furthermore, the nonlinear optical crystal strontium lithium silicon sulfur belongs to a tetragonal crystal system, and the valence of Sr atom, Li atom, Si atom and S atom in the crystal structure is +2, +1, +4 and-2 respectively; the crystal is prepared from [ LiS4]、[SiS4]And [ SrS ]8]The group constitutes a structural motif in which the Li atom forms [ LiS ] with the adjacent four S atoms4]A tetrahedral structure; the Si atom also forms [ SiS ] with its neighboring four S atoms4]A tetrahedron; [ LiS ]4]The tetrahedrons form a layered structure with a common vertex connection, with layers of [ SiS4]Tetrahedron connection forms a ring-shaped pore passage; the Sr atom is inlaid in [ LiS4]And [ SiS4]In the ring-shaped pore canal formed by tetrahedral link, 8 coordinated SrS is formed8]A dodecahedron.
Furthermore, the nonlinear optical crystal strontium lithium silicon sulfur is a middle and far infrared nonlinear optical crystal, the band gap of the nonlinear optical crystal is 3.94 eV, the infrared cut-off edge is 20 mu m, and the laser damage threshold is about AgGaS221 times of the optical effect, the nonlinear optical effect is strong: under the irradiation of 2.09 mu m fundamental frequency light, the frequency doubling capability of the crystal powder sample is commercial crystal AgGaS within the range of the granularity of 200-250 mu m2About 0.4 times of KH2PO4(KDP) 13 times higher.
The fourth purpose of the invention is realized by the following steps:
the preparation method of the nonlinear optical crystal strontium-lithium-silicon-sulfur comprises the following steps:
(a) SrS and Li with the molar ratio of 1: 1-5: 12S and SiS2The raw materials are mixed evenly and put into a graphite crucible and then a quartz glass tube, and the vacuum degree is 10-5~10-1Vacuumizing under the condition of Pa, and then sealing;
(b) putting the sealed quartz glass tube in the step (a) into a high-temperature sintering furnace, heating to 400-700 ℃, and preserving heat for 7-15 h; then heating to 750-950 ℃, and preserving the heat for 70-110 h; and cooling to room temperature to obtain the nonlinear optical crystal strontium lithium silicon sulfur.
In the step (a), SrS and Li are weighed in an airtight container with water content and oxygen content of 0.01-0.2 ppm2S and SiS2Raw materials; preferably, the airtight container is a glove box filled with an inert gas, preferably argon.
In the step (b), preferably, the temperature is increased to 400-700 ℃ at the temperature increase rate of 20-40 ℃/h; preferably, the temperature is increased to 750-950 ℃ at the temperature increase rate of 25-40 ℃/h; preferably, cooling to room temperature at the rate of 2-7 ℃/h.
The fifth purpose of the invention is realized by the following steps:
the nonlinear optical crystal strontium lithium silicon sulfur is applied to the preparation of mid-far infrared band laser frequency doubling crystals, infrared communication devices and infrared laser guidance devices.
The invention successfully prepares a new compound strontium-lithium-silicon-sulfur and a mid-far infrared nonlinear optical crystal strontium-lithium-silicon-sulfur by adopting a high-temperature solid-phase synthesis method, wherein the crystal is prepared from [ LiS4]、[SiS4]And [ SrS ]8]The group constitutes a structural element, has excellent optical performance, and has longer infrared absorption cut-off edge, wide band gap, high laser damage threshold and large nonlinear optical coefficient. As a novel middle and far infrared nonlinear optical crystal, the crystal has wide potential application value in a high-power infrared laser system.
Drawings
FIG. 1 is a powder XRD pattern of a nonlinear optical crystal of strontium lithium silicon sulfide, wherein a curve a is an experimental value and a curve b is a theoretical value.
FIG. 2 is a schematic structural diagram of a nonlinear optical crystal of strontium lithium silicon sulfide.
FIG. 3 is a band gap diagram of a nonlinear optical crystal of strontium lithium silicon sulfide.
FIG. 4 is an infrared spectrum of strontium lithium silicon sulfide as a nonlinear optical crystal.
Fig. 5 is a schematic diagram of a nonlinear optical system when a nonlinear optical crystal strontium lithium silicon sulfur is applied as a frequency doubling crystal, wherein 1, a laser, 2, an all-focusing lens, 3, strontium lithium silicon sulfur crystal powder, 4, an emergent light beam, 5, and a filter.
FIG. 6 is a graph of the frequency doubled intensity of the nonlinear optical crystal strontium lithium silicon sulfide versus the sample particle size.
Fig. 7 is a powder XRD pattern of the non-linear optical crystal strontium lithium silicon sulfide prepared in comparative example 1, in which curve a is an experimental value and curve b is a theoretical value.
Detailed Description
The invention is further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention in any way.
Procedures and methods not described in detail in the following examples are conventional methods well known in the art, and the reagents used in the examples are either analytically or chemically pure and are either commercially available or prepared by methods well known to those of ordinary skill in the art. The following examples all achieve the objects of the present invention.
Example 1
In a glove box having a water content and an oxygen content of 0.01 ppm and filled with argon as an inert gas, 0.119 g of SrS and 0.046 g of Li as starting materials were weighed2S and 0.092 g SiS2Grinding the weighed raw materials uniformly in a mortar according to the molar ratio of 1: 1, placing the ground raw materials into a clean graphite crucible, placing the graphite crucible into a quartz glass tube with the length of 20cm and the diameter of 10 mm, and placing the quartz glass tube filled with the raw materials in a vacuum degree of 10-3Vacuumizing under the condition of Pa, and then sealing; heating the sealed quartz glass tube from room temperature to 400 ℃ at the heating rate of 30 ℃/h, preserving heat for 10 h, heating to 800 ℃ at the temperature of 30 ℃/h, preserving heat for 80 h, and reacting the components in the raw material composition to obtain a compound; finally cooling down to the room at the rate of 5 ℃/hTaking out the sample, putting the sample into a mortar for grinding to obtain colorless transparent small particles SrLi2SiS4And (3) powder.
Performing powder X-ray diffraction analysis on the obtained strontium-lithium-silicon-sulfur powder, and analyzing the obtained X-ray diffraction spectrogram and SrLi analyzed by using a single crystal structure2SiS4The results of the theoretical X-ray spectrum are shown in fig. 1. As can be seen from FIG. 1, the experimental values and SrLi analyzed with a single crystal structure2SiS4The theoretical values of the theoretical X-ray spectrogram are consistent, and the crystal is pure-phase strontium-lithium-silicon-sulfur.
The structure of the crystal is schematically shown in FIG. 2, and the valences of Sr atom, Li atom, Si atom and S atom in the crystal structure are +2, +1, +4 and-2 respectively; with [ LiS ]4]、[SiS4]And [ SrS ]8]The groups form a structural element: li atom forms [ LiS ] with adjacent four S atoms4]A tetrahedral structure; the Si atom also forms [ SiS ] with its adjacent four S atoms4]A tetrahedron; [ LiS ]4]The tetrahedrons form a layered structure with a common vertex connection, with layers of [ SiS4]Tetrahedron connection forms a ring-shaped pore passage; the Sr atom is inlaid in [ LiS4]And [ SiS4]In the ring-shaped pore canal formed by tetrahedral link, 8 coordinated SrS is formed8]A dodecahedron.
The band gap of the obtained strontium lithium silicon sulfur crystal was measured by an ultraviolet-visible-near infrared diffuse reflection spectrometer, and the result is shown in fig. 3. It can be seen from the figure that the band gap of the nonlinear optical crystal strontium lithium silicon sulfide is 3.94 eV, compared with the band gap of the silver gallium sulfide (AgGaS)2) The band gap of the crystal is 2.64 eV, and the compound has a wider band gap.
The obtained strontium lithium silicon sulfur crystal is subjected to infrared spectrum characterization, and the obtained result is shown in figure 4. As can be seen from the figure, the infrared absorption cut-off edge of the nonlinear optical crystal strontium lithium silicon sulfide is longer.
Example 2
Starting materials SrS Li were weighed in a glove box filled with argon as an inert gas, having a water content and an oxygen content of 0.01 ppm2S:SiS2The mol ratio of the three components is 1: 2: 1, the components are evenly ground in a mortar and then put into a clean graphite cruciblePlacing into a quartz glass tube with a length of 20cm and a diameter of 10 mm, and placing the quartz glass tube containing the raw material in a vacuum degree of 10-3Vacuumizing under the condition of Pa, and then sealing; then heating the sealed quartz glass tube from room temperature to 400 ℃ at the temperature rise rate of 20 ℃/h, preserving heat for 7 h, then heating to 750 ℃ at the temperature of 30 ℃/h, and preserving heat for 70 h; finally cooling to room temperature at the speed of 2 ℃/h, taking out the graphite crucible to obtain the colorless transparent small SrLi particles2SiS4And (3) single crystal, wherein the single crystal is a strontium lithium silicon sulfur crystal through single crystal X-ray diffraction analysis.
Example 3
Starting materials SrS Li were weighed in a glove box filled with argon as an inert gas and having a water content and an oxygen content of 0.05 ppm2S:SiS2Grinding in a mortar at a molar ratio of 1: 3: 1, placing into a clean graphite crucible, placing into a quartz glass tube with a length of 20cm and a diameter of 10 mm, and placing the quartz glass tube with raw materials in a vacuum degree of 10-3Vacuumizing under the condition of Pa, and then sealing; then heating the sealed quartz glass tube from room temperature to 600 ℃ at the heating rate of 40 ℃/h, preserving heat for 10 h, heating to 900 ℃ at the temperature of 30 ℃/h, and preserving heat for 80 h; finally cooling to room temperature at the rate of 4 ℃/h, taking out the graphite crucible to obtain the colorless transparent small SrLi particles2SiS4And (3) single crystal.
Example 4
Starting materials SrS Li were weighed in a glove box filled with argon as an inert gas and having a water content and an oxygen content of 0.15 ppm2S:SiS2Grinding in a mortar at a molar ratio of 1: 4: 1, placing into a clean graphite crucible, placing into a quartz glass tube with a length of 20cm and a diameter of 10 mm, and placing the quartz glass tube with raw materials in a vacuum degree of 10-2Vacuumizing under the condition of Pa, and then sealing; then heating the sealed quartz glass tube from room temperature to 600 ℃ at the heating rate of 38 ℃/h, preserving the heat for 15h, and then heating to 900 ℃ at the temperature of 40 ℃/h, and preserving the heat for 100 h; finally cooling to room temperature at the speed of 6.5 ℃/h, taking out the graphite crucible to obtain the colorless transparent small SrLi particles2SiS4And (3) single crystal.
Example 5
Starting materials SrS Li were weighed in a glove box filled with argon as an inert gas and having a water content and an oxygen content of 0.2 ppm2S:SiS2Grinding in a mortar at a molar ratio of 1: 5: 1, placing into a clean graphite crucible, placing into a quartz glass tube with a length of 20cm and a diameter of 10 mm, and placing the quartz glass tube with raw materials in a vacuum degree of 10-1Vacuumizing under the condition of Pa, and then sealing; then heating the sealed quartz glass tube from room temperature to 650 ℃ at the temperature rise rate of 35 ℃/h, preserving heat for 15h, then heating to 950 ℃ at the temperature of 35 ℃/h, and preserving heat for 110 h; finally cooling to room temperature at the speed of 7 ℃/h, taking out the graphite crucible to obtain the colorless transparent small SrLi particles2SiS4And (3) single crystal.
Example 6
FIG. 5 is a schematic diagram of a nonlinear optical system when the nonlinear optical crystal strontium lithium silicon sulfur is used as a frequency doubling crystal. According to the optical system shown in fig. 5, any one of the strontium lithium silicon sulfur mid-infrared nonlinear optical crystals obtained in examples 1 to 5 is placed on the position of strontium lithium silicon sulfur crystal powder 3, an infrared beam with a wavelength of 2090 nm emitted by a Q (Ho: Tm: Cr: YAG) laser 1 is emitted as a light source at room temperature, and is incident on the strontium lithium silicon sulfur nonlinear optical crystal through a holo-lens 2 to generate a frequency doubling light with a wavelength of 1045 nm, an emergent beam 4 contains the infrared light with the wavelength of 2090 nm and the light with the wavelength of 1045 nm, and the frequency doubling light with the wavelength of 1045 nm is obtained after being filtered by a filter 5.
Measuring the relation between the frequency doubling intensity of the nonlinear optical crystal strontium-lithium-silicon-sulfur and the granularity of a sample, and using AgGaS with the same granularity (the granularity range is 200-250 mu m)2The crystal was used as a control, and the results are shown in FIG. 6. As can be seen from FIG. 6, the output intensity of the nonlinear optical crystal strontium lithium silicon sulfur is AgGaS under the condition of the same granularity20.4 times of the crystal, which is about 13 times of the KDP crystal.
Meanwhile, a 1064 nm laser is adopted to irradiate the strontium-lithium-silicon-sulfur and AgGaS2A microcrystalline sample, observing the color change of the surface of the sample to judge whether the crystal is damaged or not, and measuring the nonlinear optical crystals of strontium-lithium-silicon-sulfur and AgGaS2The laser damage threshold of the crystal was obtained and the results are shown in table 1.
TABLE 1 SrLi2SiS4And AgGaS2(as reference) laser damage threshold comparison
*AGS = AgGaS2
As can be seen from Table 1, the nonlinear optical crystalline strontium lithium silicon sulfur powder sample exhibited a high laser damage threshold, about AgGaS, under irradiation with a 1064 nm laser2The crystal is 21 times that of the strontium-lithium-silicon-sulfur crystal, so that the strontium-lithium-silicon-sulfur crystal has excellent optical performance and has wider potential application value in a high-power laser system.
Comparative example 1
Starting materials 0.119 g of SrS and 0.321 g of Li were weighed in a glove box having a water content and an oxygen content of 0.01 ppm and filled with argon as an inert gas2S and 0.092 g SiS2Grinding the weighed raw materials uniformly in a mortar according to the molar ratio of 1: 7: 1, placing the ground raw materials into a clean graphite crucible, placing the graphite crucible into a quartz glass tube with the length of 20cm and the diameter of 10 mm, and placing the quartz glass tube filled with the raw materials in a vacuum degree of 10-3Vacuumizing under the condition of Pa, and then sealing; heating the sealed quartz glass tube from room temperature to 400 ℃ at the heating rate of 30 ℃/h, preserving heat for 10 h, heating to 800 ℃ at the temperature of 30 ℃/h, preserving heat for 80 h, and reacting the components in the raw material composition to obtain a compound; finally cooling to room temperature at the rate of 5 ℃/h, taking out the sample, putting the sample into a mortar, and grinding to obtain SrLi2SiS4And (3) powder.
The strontium lithium silicon sulfur prepared in comparative example 1 was subjected to powder XRD characterization, and the obtained results are shown in fig. 7. As can be seen from FIG. 7, the presence of Li in the strontium lithium silicon sulfide crystal obtained in comparative example 14SiS4Impurities.
The strontium lithium silicon sulfur crystal prepared in comparative example 1 was subjected to optical property test, and the obtained results are shown in table 2.
TABLE 2
It can be seen from table 2 that the frequency doubling effect of the strontium lithium silicon sulfur crystal prepared in comparative example 1 is reduced by about half, and the introduced impurities affect the nonlinear optical properties of the crystal.
Claims (10)
1. The strontium lithium silicon sulfur compound is characterized in that the chemical formula is SrLi2SiS4The strontium lithium silicon sulfur compound is a strontium lithium silicon sulfur crystal, is a non-centrosymmetric monocrystal, belongs to a tetragonal system, and has a space group ofI-42mUnit cell parameters are a = b = 6.469(3) Å, c = 7.689(7) Å = β = γ =90 °, Z = 2, unit cell volume V = 321.8(4) Å3。
2. A method of preparing a strontium lithium silicon sulfide compound according to claim 1, comprising the steps of:
(a) SrS and Li with the molar ratio of 1: 1-5: 12S and SiS2Mixing the raw materials, placing into a reaction container, and keeping the vacuum degree at 10-5~10-1Vacuumizing under the condition of Pa, and then sealing;
(b) putting the sealed reaction container in the step (a) into a high-temperature sintering furnace, heating to 400-700 ℃, and preserving heat for 7-15 hours; then heating to 750-950 ℃, and preserving the heat for 70-110 h; and cooling to room temperature to obtain the strontium lithium silicon sulfur compound.
3. The method of claim 2, wherein in the step (a), the SrS and the Li are weighed in a hermetic container with a water content and an oxygen content of 0.01-0.2 ppm2S and SiS2Raw materials.
4. The strontium-lithium-silicon-sulfur nonlinear optical crystal is characterized in that the chemical formula is SrLi2SiS4Molecular weight is 257.83, it is colorless transparent single crystal with non-central symmetrical structure, and space group isI-42mUnit cell parameters are a = b = 6.469(3) Å, c = 7.689(7) Å = β = γ =90 °, Z = 2, unit cell volume V = 321.8(4) Å3。
5. The crystal of strontium lithium silicon sulfide as claimed in claim 4, wherein the crystal is tetragonal system, with [ LiS ]4]、[SiS4]And [ SrS ]8]The groups constitute structural motifs.
6. The strontium lithium silicon sulfide nonlinear optical crystal of claim 4, wherein the strontium lithium silicon sulfide nonlinear optical crystal is a mid-far infrared nonlinear optical crystal with a band gap of 3.94 eV.
7. The method for preparing the nonlinear optical crystal strontium lithium silicon sulfide as claimed in claim 4, characterized by comprising the following steps:
(a) SrS and Li with the molar ratio of 1: 1-5: 12S and SiS2Mixing the raw materials, placing into a reaction container, and keeping the vacuum degree at 10-5~10-1Vacuumizing under the condition of Pa, and then sealing;
(b) putting the sealed reaction container in the step (a) into a high-temperature sintering furnace, heating to 400-700 ℃, and preserving heat for 7-15 hours; then heating to 750-950 ℃, and preserving the heat for 70-110 h; and cooling to room temperature to obtain the nonlinear optical crystal strontium lithium silicon sulfur.
8. The method for preparing strontium lithium silicon sulfide as nonlinear optical crystal according to claim 7, wherein SrS and Li are weighed in a hermetic container with water content and oxygen content of 0.01-0.2 ppm2S and SiS2Raw materials.
9. The method for preparing the nonlinear optical crystal strontium lithium silicon sulfide as claimed in claim 7, wherein in the step (b), the temperature is raised to 400-700 ℃ at a temperature raising rate of 20-40 ℃/h; heating to 750-950 ℃ at a heating rate of 25-40 ℃/h.
10. The nonlinear optical crystal strontium lithium silicon sulfur as claimed in claim 4 is applied to the preparation of mid-far infrared band laser frequency doubling crystals, infrared communication devices or infrared laser guidance devices.
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