A series of alkaline earth metal magnesium-based sulfide (selenium) compounds and their nonlinear optical crystals and their preparation methods and uses

Abstract

The present invention relates to alkaline earth metal magnesium-based sulfide (selenium) compounds and alkaline earth metal magnesium-based sulfide (selenium) nonlinear optical crystals and preparation methods and uses thereof. The chemical formula of the series of compounds and crystals is AMg. 6 Ga 6 Q 16 , where A = Ca, Sr, Ba, Pb; Q = S, Se, all belong to the hexagonal system, and the space group #imgabs0# unit cell parameters are #imgabs1##imgabs2#α=β=90°, γ=120°, Z=3. Alkaline earth metal magnesium-based chalcogen (selenium) compounds are synthesized by vacuum high-temperature solid-phase reaction method, and alkaline earth metal magnesium-based chalcogen (selenium) crystals are grown by high-temperature solution method or Bridgman method. This material can be used to manufacture second harmonic generators, up and down frequency converters, optical parametric oscillators, etc.

Description

Technical Field

[0001] The present invention relates to a novel series of alkaline earth metal magnesium-based sulfide (selenium) compounds and nonlinear optical crystals thereof. The molecular formula of the alkaline earth metal magnesium-based sulfide (selenium) compounds and crystals thereof is AMg6Ga6Q 16 , wherein A=Ca, Sr, Ba, Pb; Q=S, Se. The preparation method of the nonlinear optical crystal and compound belongs to the field of optical technology and crystal material technology. Background Art

[0002] In recent years, the research on new nonlinear optical crystal materials with large mid- and far-infrared frequency doubling effect, wide transmission band, large optical damage threshold, and stable physical and chemical properties has gradually become a hot topic. The main nonlinear optical materials are: β-BaB2O4 (BBO) crystal, LiB3O5 (LBO) crystal, CsB3O5 (CBO) crystal, CsLiB6O 10 (CLBO) crystal, KBe2BO3F2 (KBBF) crystal, AgGaS2 (AGS) crystal, AgGaSe2 (AGSe) crystal and ZnGeP2 (ZGP) crystal. Although the crystal growth technology of these materials has become increasingly mature, there are still obvious shortcomings: such as easy deliquesce of crystals, long growth cycle, serious layered growth habits, high price, low laser damage threshold and two-photon absorption. Therefore, finding new nonlinear optical crystal materials is still a very important and arduous task.

[0003] Chalcogenide crystals are important semiconductor materials and mid-infrared materials. Their performance has attracted wide attention and they are widely used in lighting, display, military security, laser medicine, etc. Due to their good comprehensive performance, they are conducive to obtaining strong nonlinear optical effects and are an ideal choice for new mid- and far-infrared nonlinear optical crystals. Summary of the invention

[0004] One of the objects of the present invention is to provide a series of alkaline earth metal magnesium-based sulfide (selenide) compounds.

[0005] The second object of the present invention is to provide a method for preparing a series of alkaline earth metal magnesium-based sulfide (selenide) compounds.

[0006] The third object of the present invention is to provide a series of alkaline earth metal magnesium-based chalcogen (selenium) infrared nonlinear optical crystals.

[0007] The fourth object of the present invention is to provide a method for preparing a series of alkaline earth metal magnesium-based chalcogen (selenium) infrared nonlinear optical crystals.

[0008] The fifth object of the present invention is to provide applications of a series of alkaline earth metal magnesium-based chalcogen (selenium) infrared nonlinear optical crystals.

[0009] One of the purposes of the present invention is achieved in that:

[0010] The present invention aims to provide a novel alkaline earth metal magnesium-based sulfide (selenium) compound, characterized in that the alkaline earth metal magnesium-based sulfide (selenium) compound has a molecular formula of AMg6Ga6Q 16 , where A=Ca, Ba, Sr, Pb; Q=S, Se, no symmetry center, hexagonal system, space group The unit cell parameters are α=β=90°,γ=120°,Z=3,unit cell volume

[0011] The second object of the present invention is achieved in this way:

[0012] The present invention provides a series of alkaline earth metal magnesium-based sulfide (selenium) compounds, which are prepared by a vacuum high-temperature solid phase reaction method according to the following chemical reaction formula:

[0013] 1) A+6Mg+6Ga+16Q→AMg6Ga6Q 16

[0014] 2) A+6MgQ+6Ga+9Q→AMg6Ga6Q 16

[0015] 3) A+6Mg+3Ga2Q3+7Q→AMg6Ga6Q 16

[0016] 4) A+6MgQ+3Ga2Q3+1Q→AMg6Ga6Q 16

[0017] 5) AQ+6Mg+3Ga2Q3+6Q→AMg6Ga6Q 16

[0018] 5) AQ+6MgQ+6Ga+9Q→AMg6Ga6Q 16

[0019] 6) AQ+6MgQ+3Ga2Q3→AMg6Ga6Q 16

[0020] In the above equations (1)-(6), A = Ca, Ba, Sr, Pb; Q = S, Se

[0021] The third object of the present invention is achieved in this way:

[0022] The present invention aims to provide a series of alkaline earth metal magnesium-based chalcogenide (selenide) nonlinear optical crystals, characterized in that the molecular formula of the series of alkaline earth metal magnesium-based chalcogenide (selenide) nonlinear optical crystals is AMg6Ga6Q 16 , where A=Ca, Sr, Ba, Pb; Q=S, Se, no symmetry center, hexagonal system, space group The unit cell parameters are α=β=90°,γ=120°,Z=3,unit cell volume

[0023] The fourth object of the present invention is achieved in this way:

[0024] The preparation method of a series of alkaline earth metal magnesium-based chalcogen (selenium) nonlinear optical crystals provided by the present invention adopts a high temperature solution method or a Bridgman method to grow a series of alkaline earth metal magnesium-based chalcogen (selenium) nonlinear optical crystals, and the specific operation is carried out according to the following steps:

[0025] In an airtight container filled with inert gas argon and having a water content and an oxygen content of 0.01-0.1 ppm, the single-phase polycrystalline powder of the alkaline earth metal magnesium-based sulfide (selenide) compound and the flux are uniformly mixed and put into a clean graphite crucible, and then put into a closed reaction container. The closed reaction container containing the raw materials is placed in a vacuum degree of 10 -5 -10 -1 Pa, vacuumize and seal, heat from room temperature to 400-600℃ at a rate of 10-50℃ / h, keep warm for 10-120 hours, then heat to 700-1200℃ at a rate of 5-40℃ / h, keep warm for 10-120 hours, obtain mixed melt, cool to room temperature at a rate of 1-10℃ / h; or place the sealed reaction container containing the mixture after vacuumization in a tubular descending furnace, slowly heat to 400-600℃ and heat at a constant temperature for 10-120 hours, then heat to 700-1200℃ and heat at a constant temperature for 10-120 hours, at this time, the crucible is descended at a rate of 0.36-2mm / h, then cool to room temperature in 10 hours, and close the furnace. After the sample is cooled, the alkaline earth metal magnesium-based sulfide (selenium) nonlinear optical crystal is obtained. The molar ratio of the single-phase polycrystalline powder of the alkaline earth metal magnesium-based sulfide (selenium) compound to the flux is 1:0.1-30.

[0026] Alternatively, a mixture of a compound containing A=Ca, Sr, Ba, Pb, a compound containing magnesium, a compound containing gallium and a compound containing Q=S, Se or a mixture of a compound containing A=Ca, Sr, Ba, Pb, a compound containing magnesium, a compound containing gallium and a compound containing Q=S, Se and a flux is directly placed in a clean graphite crucible in a glove box filled with an inert gas argon and having a water content and an oxygen content of 0.01-0.1 ppm, and then placed in a sealed reaction container, and the sealed reaction container containing the raw materials is placed in a vacuum degree of 10 -5 -10 -1 Pa, vacuumize and seal, heat from room temperature to 400-600℃ at a rate of 10-50℃ / h, keep warm for 10-120 hours, then heat to 700-1200℃ at a rate of 5-40℃ / h, keep warm for 10-120 hours, obtain mixed melt, cool to room temperature at a rate of 1-10℃ / h; or place the sealed reaction container containing the mixture after vacuumization in a tubular descending furnace, slowly heat to 400-600℃ and heat at a constant temperature for 10-120 hours, then heat to 700-1200℃ and heat at a constant temperature for 10-120 hours, at this time, the crucible is descended at a rate of 0.36-2mm / h, then cool to room temperature in 10 hours, and close the furnace. After the sample is cooled, the nonlinear optical crystal of alkaline earth metal magnesium-based sulfide (selenium) compound is obtained. The molar ratio of the compound containing A=Ca, Sr, Ba, Pb, the compound containing magnesium, the compound containing gallium and the compound containing Q=S, Se to the flux is 0.8-1.2:5.8-6.2:5.8-6.2:15.8-16.2:0.1-30;

[0027] The main self-help melts mentioned are Se, S, Ba, Mg, Ga, CaS, SrS, BaS, PbS, MgS, Ga2S3, and the help melts are similar to CaS-S, CaSe-Se, CaS-Ga. 2S3, CaS-Ga2Se3, CaSe-Ga2S3, CaSe-Ga2Se3, CaS-MgS, CaSe-MgSe, CaS-S-MgS, CaSe-Se-MgSe, CaS- S-Ga2S3, CaSe-Se-Ga2Se3, Mg-S, MgS-S, MgSe-Se, SrS-MgS, SrSe-MgSe, SrS-S, SrS-Se, SrS-Ga2S3, SrSe-Ga2Se3, SrS-S-Ga2S3, SrSe-Se-Ga2Se3, Ba-S, Ba-Se, Ba-Ga2S3, Ba-Ga2Se3, Ba-MgS, Ba-MgSe, BaS-MgS, BaSe-MgSe, BaS-S, BaS-Se, BaS-Ga2S3, BaSe-Ga2Se3, Ba-Ga-S, Ba-Ga-Se, Ba-S-Ga2S3, Ba -Se-Ga2Se3, BaS-S-Ga2S3, BaSe-Se-Ga2Se3, BaS-S-MgS, BaSe-Se-MgSe, Pb-S, Pb-Se, Pb-Ga2S3, Pb -Ga2Se3, Pb-MgS, Pb-MgSe, PbS-MgS, PbSe-MgSe, PbS-S, PbS-Se, PbS-Ga2S3, PbSe-Ga2Se3, Pb-Ga-S , Pb-Ga-Se, Pb-S-Ga2S3, Pb-Se-Ga2Se3, PbS-S-Ga2S3, PbSe-Se-Ga2Se3, PbS-S-MgS, PbSe-Se-MgSe.

[0028] The molar ratio of CaS to S in the flux CaS-S system used is 2-7:1-10; the molar ratio of CaSe to Se in the CaSe-Se system is 2-7:1-10; the molar ratio of CaS to Ga2S3 in the CaS-Ga2S3 system is 0.5-7:1-6; the molar ratio of CaSe to Ga2S3 in the CaSe-Ga2Se3 system is 0.5-7:1-4; the molar ratio of CaS to MgS in the CaS-MgS system is 2-7:1-10; the molar ratio of CaSe to MgSe in the CaSe-MgSe system is 2-7:1-10; the molar ratio of CaS, S and MgS in the CaS-S-MgS system is 2-5:1-10:1-3; CaS The molar ratio of CaS, Se and MgSe in the e-Se-MgSe system is 2-5:1-10:1-3; the molar ratio of CaSe, Se and Ga2Se in the CaSe-S-Ga2Se3 system is 2-7:1-10:1-6; the molar ratio of Mg to S in the Mg-S system is 2-5:1-10; the molar ratio of Mg to S in the MgS-S system is 2-5:1-10; the molar ratio of Mg to S in the MgSe-Se system is 2-5:1-10; the molar ratio of SrS to S in the SrS-S system is 2-5:1-10; the molar ratio of SrSe to Se in the SrSe-Se system is 2-5:1-10; the molar ratio of SrS to Ga2S3 in the SrS-Ga2S3 system is 1 -4:1-10; the molar ratio of SrSe to Ga2S3 in the SrSe-Ga2Se3 system is 1-4:1-10; the molar ratio of SrS, S to Ga2S3 in the SrS-S-Ga2S3 system is 2-5:1-10:1-3; the molar ratio of SrSe, Se to Ga2Se3 in the SrSe-Se-Ga2Se3 system is 2-5:1-10:1-3; the molar ratio of Ba to S in the Ba-S system is 2-5:1-6; the molar ratio of Ba to Se in the Ba-Se system is 2-5:1-6; the molar ratio of Ba to Ga2S3 in the Ba-Ga2S3 system is 2-5:1-6; the molar ratio of Ba to Ga2Se3 in the Ba-Ga2Se3 system is 2-5:1 -6; the molar ratio of Ba to MgS in the Ba-MgS system is 2-5:1-6; the molar ratio of Ba to MgSe in the Ba-MgSe system is 2-5:1-6; the molar ratio of BaS to MgS in the BaS-MgS system is 2-5:1-6; the molar ratio of BaSe to MgSe in the BaSe-MgSe system is 2-5:1-6; the molar ratio of BaS to S in the BaS-S system is 2-5:1-6; the molar ratio of BaSe to Se in the BaSe-Se system is 2-5:1-6; the molar ratio of BaS to Ga2S3 in the BaS-Ga2S3 system is 2-5:1-6; the molar ratio of BaSe to Ga2Se3 in the BaSe-Ga2Se3 system is 2-5:1-6;The molar ratio of Ba, Ga and S in the Ba-Ga-S system is 2-5:1-4:1-10; the molar ratio of Ba, Ga and Se in the Ba-Ga-Se system is 2-5:1-4:1-10; the molar ratio of Ba, S and Ga2S3 in the Ba-S-Ga2S3 system is 2-5:1-4:1-10; the molar ratio of Ba, S and Ga2S3 in the Ba-Se-Ga2Se3 system is 2-5:1-4:1-10; the molar ratio of BaS, S and MgS in the BaS-S-MgS system is 2-5:1-4:1-10; the molar ratio of BaSe, Se and The molar ratio of Pb to MgSe is 2-5:1-4:1-10; the molar ratio of Pb to S in the Pb-S system is 2-5:1-6; the molar ratio of Pb to Se in the Pb-Se system is 2-5:1-6; the molar ratio of Pb to Ga2S3 in the Pb-Ga2Se3 system is 2-5:1-6; the molar ratio of Pb to Ga2Se3 in the Pb-MgS system is 2-5:1-6; the molar ratio of Pb to MgSe in the Pb-MgSe system is 2-5:1-6; the molar ratio of PbS to S in the PbS-S system is 2-5:1-6 ; The molar ratio of PbSe to Se in the PbSe-Se system is 2-5:1-6; the molar ratio of PbS to Ga2S3 in the PbS-Ga2S3 system is 2-5:1-6; the molar ratio of PbSe to Ga2Se3 in the PbSe-Ga2Se3 system is 2-5:1-6; the molar ratio of Pb, Ga and S in the Pb-Ga-S system is 2-5:1-4:1-10; the molar ratio of Pb, Ga and Se in the Pb-Ga-Se system is 2-5:1-4:1-10; the molar ratio of Pb, S and Ga2S3 in the Pb-S-Ga2S3 system is 2-5:1-4:1-10; The molar ratio of Pb, Se and Ga2Se3 in Se-Ga2Se3 system is 2-5:1-4:1-10; the molar ratio of PbS, S and Ga2S3 in PbS-S-Ga2S3 system is 2-5:1-4:1-10; the molar ratio of PbSe, Se and Ga2Se3 in PbSe-Se-Ga2Se3 system is 2-5:1-4:1-10; the molar ratio of PbS, S and MgS in PbS-S-MgS system is 2-5:1-4:1-10; the molar ratio of PbSe, Se and MgSe in PbSe-Se-MgeS system is 2-5:1-4:1-10;

[0029] The fifth purpose of the present invention is achieved in this way:

[0030] The above series of alkaline earth metal magnesium-based chalcogen (selenium) crystals are suitable for mid- and far-infrared laser frequency doubling crystals, infrared communication devices, and infrared laser guidance devices. They can also be used to prepare frequency doubling generators, up or down frequency converters, or optical parametric oscillators. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 is the compound CaMg6Ga6S prepared in the present invention 16 Theoretical X-ray spectrum of the crystal.

[0032] Figure 2 The CaMg6Ga6S 16 Crystal structure diagram;

[0033] Figure 3 The working principle diagram of the nonlinear optical device made by the present invention, wherein 1 is the laser, 2 is the emitted light beam, and 3 is AMg6Ga6Q 16 , wherein A=Ca, Sr, Ba, Pb; Q=S, Se, a nonlinear optical crystal, 4 is the output light beam, and 5 is the filter. DETAILED DESCRIPTION

[0034] The present invention is described in detail below with reference to the accompanying drawings and implementation examples, but is not limited to the described embodiments.

[0035] Example 1

[0036] According to the reaction formula: 1CaS+6MgS+3Ga2S3→CaMg6Ga6S 16 , synthesized CaMg6Ga6S 16 Compound:

[0037] In a glove box filled with inert gas argon and containing 0.05 ppm of water and oxygen respectively, the starting materials were weighed in a molar ratio of CaS:MgS:Ga2S3 of 1:6:3, mixed evenly and ground carefully in a mortar, then placed in a clean graphite crucible, and then the graphite crucible was placed in a quartz tube, and the quartz tube was evacuated to 10 -1 Pa and melt-seal it. Put the sealed quartz tube into a pit muffle furnace and heat it to 700℃ at a rate of 30℃ / h, keep it for 10h, then heat it to 1100℃ at a rate of 30℃ / h, keep it for 100h, and then cool it to room temperature at a rate of 7.5℃ / h to obtain the compound CaMg6Ga6S 16 The single-phase polycrystalline powder was subjected to X-ray analysis, and the obtained X-ray spectrum was similar to that of CaMg6Ga6S 16 The X-ray spectra obtained from the single crystal structure are consistent.

[0038] The above single-phase polycrystalline powder was carefully ground in a mortar, and then placed in a clean graphite crucible. The graphite crucible was then placed in a quartz tube, and the quartz tube was evacuated to 10 -3Pa and melt-seal the quartz tube, put it into a pit muffle furnace, raise the temperature to 600℃ at a rate of 10℃ / h, keep it warm for 10h, then raise the temperature to 1200℃ at a rate of 10℃ / h. After the raw materials are melted, keep it warm for 120h, and then cool it to room temperature at a rate of 3℃ / h to obtain CaMg6Ga6S 16 Crystal; or the above single-phase polycrystalline powder is carefully ground in a mortar, and the sealed reaction container is placed in a tubular growth descending furnace and slowly heated to 500-700°C, kept warm for 40-50 hours, and then heated to 1200°C, kept warm for 100-120 hours, at which time the crucible is lowered at a rate of 0.36-1.2mm / h, and then cooled to 300°C in 100-120 hours, and the furnace is closed and cooled to room temperature. After the sample is cooled, the graphite crucible is taken out to obtain CaMg6Ga6S 16 Crystal.

[0039] Example 2

[0040] According to the reaction formula: 1CaS+6MgS+6Ga+9S→CaMg6Ga6S 16 ,synthesis

[0041] CaMg6Ga6S 16 Compound:

[0042] In a glove box filled with inert gas argon and having a water content and an oxygen content of 0.05 ppm respectively, CaS, MgS, Ga, and S were directly weighed in a molar ratio of 1:6:6:9, the weighed raw materials were mixed evenly and placed in a clean graphite crucible, and then the graphite crucible was placed in a quartz tube, and the quartz tube was evacuated to 10 -5 Pa and melt-seal it, put the sealed quartz tube into a pit muffle furnace, raise the temperature to 600℃ at a rate of 50℃ / h, keep it for 120h, then raise the temperature to 1200℃ at a rate of 40℃ / h, keep it for 150h, and then cool it to room temperature at a rate of 10℃ / h to obtain CaMg6Ga6S 16 Crystal.

[0043] Example 3

[0044] According to the reaction formula: 1SrS+6MgS+3Ga2S3→SrMg6Ga6S 16 , synthesized SrMg6Ga6S 16 Compound:

[0045] In a glove box filled with inert gas argon and containing 0.05 ppm of water and oxygen respectively, the starting materials were weighed in a molar ratio of SrS:MgS:Ga2S3 of 1:6:3, the weighed materials were mixed evenly and ground carefully in a mortar, and then placed in a clean graphite crucible, and the graphite crucible was placed in a quartz tube, and the quartz tube was evacuated to 10 -2 Pa and melt-seal the tube. Put the sealed quartz tube into a pit muffle furnace and heat it to 600℃ at a rate of 20℃ / h, keep it for 30h, then heat it to 1200℃ at a rate of 40℃ / h, keep it for 100h, and then cool it to room temperature at a rate of 8℃ / h to obtain polycrystalline powder. X-ray analysis of the product shows that the obtained X-ray spectrum is consistent with that of SrMg6Ga6S 16 The X-ray spectra obtained from the single crystal structure are consistent.

[0046] The above single-phase polycrystalline powder is carefully ground in a mortar and placed in a graphite crucible. It is pressed and covered with a medicine spoon and placed in a quartz ampoule. The sealed reaction container is placed in a tubular growth descending furnace and slowly heated to 500-700°C, kept warm for 40-50 hours, and then heated to 1200°C and kept warm for 100-120 hours. At this time, the crucible is lowered at a rate of 0.36-1.2 mm / h, and then cooled to 300°C in 100-120 hours, and the furnace is turned off and cooled to room temperature. After the sample is cooled, the graphite crucible is taken out to obtain SrMg6Ga6Se 16 Crystal.

[0047] Example 4

[0048] According to the reaction formula: 1SrS+6Mg+3Ga2S3+9S→SrMg6Ga6S 16 , synthesis of SrMg6Ga6Se 16 Compound:

[0049] In a glove box filled with inert gas argon and with a water content and oxygen content of 0.05 ppm respectively, SrS, Mg, Ga2S3, and S were weighed directly in a molar ratio of 1:6:3:9, mixed evenly, and put into a clean graphite crucible, and then the graphite crucible was put into a quartz ampoule. After 6 hours of vacuuming, the internal pressure of the quartz ampoule was about 10 -5 Pa, the tube was sealed with hydrogen-oxygen flame and placed in a growth furnace, slowly heated to 600°C and kept at constant temperature for 120 hours, then heated to 1200°C to melt the raw materials and kept at constant temperature for 10 hours. At this time, the crucible was lowered at a rate of 2 mm / h, and then cooled to room temperature in 10 hours, and the furnace was closed. After the sample was cooled, SrMg6Ga6S 16 Single crystal.

[0050] Example 5

[0051] According to the reaction formula: 1BaS+6Mg+3Ga2S3+9S→BaMg6Ga6S 16 , synthesized BaMg6Ga6S 16 Compound:

[0052] In a glove box filled with inert gas argon and having a water content and an oxygen content of 0.05 ppm respectively, the starting materials were weighed in a molar ratio of BaS, Mg, Ga2S3, and S of 1:6:3:9, and the weighed raw materials were mixed with a flux BaS-S in a molar ratio of 1:5, wherein the molar ratio of BaS to S was 2:1. After being mixed evenly, they were put into a clean graphite crucible, and then the graphite crucible was put into a quartz tube, and the quartz tube was evacuated to 10 -2 Pa and melt-seal it, put the sealed quartz tube into a pit muffle furnace, raise the temperature to 600℃ at a rate of 20℃ / h, keep it for 20h, then raise the temperature to 1110℃ at a rate of 40℃ / h, keep it for 150h, and then cool it to room temperature at a rate of 5℃ / h to obtain BaMg6Ga6S 16 Polycrystalline powder. The product was subjected to X-ray analysis, and the obtained X-ray spectrum was similar to that of BaMg6Ga6S 16 The X-ray spectra obtained from the single crystal structure are consistent.

[0053] The above single-phase polycrystalline powder was placed in a clean graphite crucible, and the graphite crucible was placed in a quartz tube, and the quartz tube was evacuated to 10 -2 Pa and melt-seal it. Put the sealed quartz tube into a pit muffle furnace and heat it to 600℃ at a rate of 20℃ / h, keep it for 20h, then heat it to 1200℃ at a rate of 40℃ / h, keep it for 100h, and then cool it to room temperature at a rate of 3℃ / h to obtain BaMg6Ga6S 16 Crystal.

[0054] Example 6

[0055] According to the reaction formula: Ba+6MgS+3Ga2S3+1S→BaMg6Ga6S 16 , synthesized BaMg6Ga6S 16 Compound:

[0056] In a glove box filled with inert gas argon and having a water content and an oxygen content of 0.05 ppm respectively, Ba, MgS, Ga2S3, and S are directly weighed in a molar ratio of 1:6:3:1, and the weighed raw materials are mixed with a flux BaS-S in a molar ratio of 1:3, wherein the molar ratio of BaS to S is 2:1. After the mixture is evenly mixed, it is put into a clean graphite crucible, and then the graphite crucible is put into a quartz tube, and the quartz tube is evacuated to 10 -5Pa and melt-sealed, placed in a growth furnace and slowly heated to 600°C and kept at a constant temperature for 120 hours, then heated to 1200°C to melt the raw materials and kept at a constant temperature for 10 hours, at which time the crucible descended at a rate of 2 mm / h, then cooled to room temperature in 10 hours, and the furnace was closed. After the sample cooled, BaMg6Ga6S 16 Crystal.

[0057] Example 7

[0058] According to the reaction formula: 1PbS+6Mg+3Ga2S3+9S→pbMg6Ga6S 16 , synthesized PbMg6Ga6S 16 Compound:

[0059] In a glove box filled with inert gas argon and having a water content and an oxygen content of 0.05 ppm respectively, the starting materials were weighed according to the molar ratio of PbS, Mg, Ga2S3, and S of 1:6:3:9, and the weighed raw materials were mixed with the flux Pb-S in a molar ratio of 1:2, wherein the molar ratio of Pb to S was 2:1. After being mixed evenly, the mixture was placed in a mortar and ground carefully, and then placed in a clean graphite crucible. The graphite crucible was placed in a quartz tube, and the quartz tube was evacuated to 10 -2 Pa and melt-seal it. Put the sealed quartz tube into a pit muffle furnace and heat it to 600℃ at a rate of 20℃ / h, keep it for 20h, then heat it to 1100℃ at a rate of 40℃ / h, keep it for 150h, and then cool it to room temperature at a rate of 8℃ / h to obtain PbMg6Ga6S 16 Polycrystalline powder. The product was subjected to X-ray analysis, and the obtained X-ray spectrum was consistent with that of PbMg6Ga6S 16 The X-ray spectra obtained from the single crystal structure are consistent.

[0060] The above single-phase polycrystalline powder was placed in a clean graphite crucible, and the graphite crucible was placed in a quartz tube, and the quartz tube was evacuated to 10 -2 Pa and melt-seal it. Put the sealed quartz tube into the growth furnace and slowly heat it to 600℃ and keep it at constant temperature for 120 hours. Then heat it to 1200℃ to melt the raw materials and keep it at constant temperature for 10 hours. At this time, the crucible descends at a rate of 2mm / h. Then it cools down to room temperature in 10 hours and the furnace is closed. After the sample is cooled, PbMg6Ga6S 16 Crystal.

[0061] Example 8

[0062] According to the reaction formula: Pb+6MgS+3Ga2S3+1S→PbMg6Ga6S 16 , synthesized PbMg6Ga6S 16 Compound:

[0063] In a glove box filled with inert gas argon and having a water content and an oxygen content of 0.05 ppm respectively, Pb, MgS, Ga2S3, and S are directly weighed in a molar ratio of 1:6:3:1, and the weighed raw materials are mixed with flux Pb-S in a molar ratio of 1:3, wherein the molar ratio of Pb to S is 2:3. After mixing evenly, the mixture is put into a clean graphite crucible, and then the graphite crucible is put into a quartz tube, and the quartz tube is evacuated to 10 -5 Pa and melt-sealed, placed in a growth furnace and slowly heated to 600°C and kept at a constant temperature for 120 hours, then heated to 1200°C to melt the raw materials and kept at a constant temperature for 10 hours, at which time the crucible descended at a rate of 2 mm / h, then cooled to room temperature in 10 hours, and the furnace was closed. After the sample cooled, PbMg6Ga6S 16 Crystal.

[0064] Embodiment 9:

[0065] The alkaline earth metal magnesium-based chalcogenide (selenide) crystals obtained in Examples 1-6 are processed into a frequency doubling device with a size of 5 mm×5 mm×6 mm in a matching direction, and the attached Figure 2 As shown, it is arranged at position 3, and an infrared light beam 2 with a wavelength of 2090nm is emitted by a laser 1 and irradiated into an alkaline earth metal magnesium-based sulfide (selenium) compound single crystal 3, generating a frequency-doubled light with a wavelength of 1045nm. The outgoing light beam 4 contains infrared light with a wavelength of 2090nm and frequency-doubled light of 1045nm, which is filtered out by a filter 5 to obtain a laser with a wavelength of 1045nm.

Claims

1. A series of alkaline earth metal magnesium-based chalcogenide and alkaline earth metal magnesium-based selenide nonlinear optical crystals, characterized in that The molecular formula of this series of alkaline earth metal magnesium-based chalcogenide and alkaline earth metal magnesium-based selenide nonlinear optical crystals is AMg6Ga6Q 16 , where A=Ca, Sr, Ba, Pb; Q=S, Se, no symmetry center, hexagonal system, space group The unit cell parameters are α=β=90°,γ=120°,Z=3, unit cell volume 2. The method for preparing a series of alkaline earth metal magnesium-based chalcogenide and alkaline earth metal magnesium-based selenide nonlinear optical crystals according to claim 1, characterized in that The process is carried out in the following steps: in an airtight container which is a glove box filled with inert gas argon and has a water content and an oxygen content of 0.01-0.1 ppm, a mixture of element A in a compound containing A=Ca, Sr, Ba, Pb, element magnesium in a compound containing magnesium, element gallium in a compound containing gallium and element Q in a compound containing Q=S, Se in a molar ratio of 0.8-1.2:5.8-6.2:5.8-6.2:15.8-16.2 is ground and placed in a clean graphite crucible, and then placed in a sealed reaction container; the sealed reaction container containing the raw materials is evacuated and sealed, and placed in a muffle furnace, calcined and then cooled to room temperature; a sample is taken out, placed in a mortar, crushed and ground, so as to obtain a series of alkaline earth metal magnesium-based sulfide and alkaline earth metal magnesium-based selenide nonlinear optical crystal single-phase polycrystalline powders.

3. The method for preparing a series of alkaline earth metal magnesium-based chalcogenide and alkaline earth metal magnesium-based selenide nonlinear optical crystals according to claim 2, characterized in that: The compound containing A=Ca, Sr, Ba, Pb includes at least one of calcium and calcium salt, at least one of strontium and strontium salt, at least one of barium and barium salt, and at least one of lead and lead salt; the calcium salt includes at least one of calcium sulfide, calcium selenide, calcium fluoride, calcium chloride, calcium bromide and calcium sulfate; the strontium salt includes at least one of strontium sulfide, strontium selenide, strontium fluoride, strontium chloride, strontium bromide and strontium sulfate; the barium salt includes at least one of barium sulfide, barium selenide, barium fluoride, barium chloride, barium bromide and barium sulfate; the lead salt includes at least one of lead sulfide, lead selenide, lead fluoride, lead chloride, lead bromide and lead sulfate; The magnesium-containing compound is at least one of magnesium element and magnesium salt; the magnesium salt includes at least one of magnesium sulfide, magnesium selenide, magnesium fluoride, magnesium chloride, magnesium bromide and magnesium sulfate; The gallium-containing compound is at least one of a single gallium substance and a gallium salt; the gallium salt includes at least one of gallium sulfide, gallium selenide, gallium fluoride, gallium chloride, gallium bromide and gallium sulfate; The Q=S, Se-containing compound includes sulfur, selenium, and at least one of calcium sulfide, strontium sulfide, barium sulfide, lead sulfide, calcium selenide, strontium selenide, barium selenide, lead selenide, magnesium sulfide, magnesium selenide, gallium sulfide and gallium selenide.

4. The method for preparing a series of alkaline earth metal magnesium-based chalcogenide and alkaline earth metal magnesium-based selenide nonlinear optical crystals as claimed in claim 3, characterized in that: A series of alkaline earth metal magnesium-based sulfide and alkaline earth metal magnesium-based selenide nonlinear optical crystals are grown by high temperature melt method or Bridgman method.

5. The method according to claim 4, characterized in that: The specific operation is as follows: a. In an airtight container filled with inert gas argon and having a water content and an oxygen content of 0.01-0.1ppm, the series of alkaline earth metal magnesium-based sulfide and alkaline earth metal magnesium-based selenium nonlinear optical crystal single-phase polycrystalline powders obtained in claim 2 or a mixture of the series of alkaline earth metal magnesium-based sulfide and alkaline earth metal magnesium-based selenium nonlinear optical crystal single-phase polycrystalline powders obtained in claim 2 and a flux are placed in a clean graphite crucible and then placed in a sealed reaction container; the sealed reaction container containing the raw materials is evacuated and sealed, and the sealed sealed reaction container is placed in a pit muffle furnace and heated to melt to obtain a mixed melt, and the temperature is lowered. Or constant temperature growth to prepare a series of alkaline earth metal magnesium-based chalcogenides and alkaline earth metal magnesium-based selenium nonlinear optical crystals; or placing a closed reaction container containing the above mixture in a tubular descending furnace, slowly descending it, so that it passes through a heating furnace with a certain temperature gradient, and controlling the furnace temperature to be slightly higher than the melting point of the compound; selecting a suitable heating zone, when the crucible passes through the heating zone, the mixture in the crucible is melted, and when the crucible continues to descend, the temperature of the bottom of the crucible first drops below the melting point and begins to crystallize, and the crystals continue to grow as the crucible descends, so as to prepare a series of alkaline earth metal magnesium-based chalcogenides and alkaline earth metal magnesium-based selenium nonlinear optical crystals; Or directly heat a mixture of a compound containing A=Ca, Sr, Ba, Pb, a compound containing magnesium, a compound containing gallium and a compound containing Q=S, Se or a mixture of a compound containing A=Ca, Sr, Ba, Pb, a compound containing magnesium, a compound containing gallium and a compound containing Q=S, Se and a flux in a glove box filled with inert gas argon and having a water content and an oxygen content of 0.01-0.1 ppm, directly heat to melt to obtain a mixed melt, cool or grow at a constant temperature to prepare a series of alkaline earth metal magnesium-based sulfides and alkaline earth metal magnesium-based selenium Nonlinear optical crystals; or placing a closed reaction container containing the above mixture in a tubular descending furnace, slowly descending it, passing through a heating furnace with a certain temperature gradient, and controlling the furnace temperature to be slightly higher than the melting point of the compound; selecting a suitable heating zone, when the crucible passes through the heating zone, the mixture in the crucible is melted, and when the crucible continues to descend, the temperature at the bottom of the crucible first drops below the melting point and begins to crystallize, and the crystals continue to grow as the crucible descends, thereby preparing a series of alkaline earth metal magnesium-based sulfide and alkaline earth metal magnesium-based selenium nonlinear optical crystals.

6. The method according to claim 5, characterized in that The molar ratio of the series of alkaline earth metal magnesium-based chalcogenide and alkaline earth metal magnesium-based selenide nonlinear optical crystal single-phase polycrystalline powder to the flux is 1:0.1-30; or the molar ratio of the compound containing A=Ca, Sr, Ba, Pb, the magnesium-containing compound, the gallium-containing compound and the sulfur-containing compound to the flux is 0.8-1.2:5.8-6.2:5.8-6.2:15.8-16.2:0.1-30; The single flux includes one of Se, S, Ca, Sr, Ba, Pb, Mg, Ga, calcium salt, strontium salt, barium salt, lead salt, magnesium salt and gallium salt; the composite flux includes CaS-S, CaSe-Se, CaS-Ga2S3, CaS-Ga2Se3, CaSe-Ga2S3, CaSe-Ga2Se3, CaS-MgS, CaSe-MgSe, CaS-S-MgS, CaSe-Se-MgSe, CaS-S-G a2S3, CaSe-Se-Ga2Se3, Mg-S, MgS-S, MgSe-Se, SrS-MgS, SrSe-MgSe, SrS-S, SrS-Se, SrS-Ga2S3, SrSe -Ga2Se3, SrS-S-Ga2S3, SrSe-Se-Ga2Se3, Ba-S, Ba-Se, Ba-Ga2S3, Ba-Ga2Se3, Ba-MgS, Ba-MgSe, BaS- MgS, BaSe-MgSe, BaS-S, BaS-Se, BaS-Ga2S3, BaSe-Ga2Se3, Ba-Ga-S, Ba-Ga-Se, Ba-S-Ga2S3, Ba-Se-G a2Se3, BaS-S-Ga2S3, BaSe-Se-Ga2Se3, BaS-S-MgS, BaSe-Se-MgSe, Pb-S, Pb-Se, Pb-Ga2S3, Pb-Ga2Se 3. One or more of Pb-MgS, Pb-MgSe, PbS-MgS, PbSe-MgSe, PbS-S, PbS-Se, PbS-Ga2S3, PbSe-Ga2Se3, Pb-Ga-S, Pb-Ga-Se, Pb-S-Ga2S3, Pb-Se-Ga2Se3, PbS-S-Ga2S3, PbSe-Se-Ga2Se3, PbS-S-MgS, and PbSe-Se-MgSe.

7. The method according to claim 6, characterized in that: The molar ratio of CaS to S in the composite flux CaS-S system is 2-7:1-10; the molar ratio of CaSe to Se in the CaSe-Se system is 2-7:1-10; the molar ratio of CaS to Ga2S3 in the CaS-Ga2S3 system is 0.5-7:1-6; the molar ratio of CaSe to Ga2S3 in the CaSe-Ga2Se3 system is 0.5-7:1-4; the molar ratio of CaS to MgS in the CaS-MgS system is 2-7:1-10; the molar ratio of CaSe to MgSe in the CaSe-MgSe system is 2-7:1-10; the molar ratio of CaS, S and MgS in the CaS-S-MgS system is 2-5:1-10:1-3; The molar ratio of CaS, Se and MgSe in the Se-Se-MgSe system is 2-5:1-10:1-3; the molar ratio of CaSe, Se and Ga2Se in the CaSe-S-Ga2Se3 system is 2-7:1-10:1-6; the molar ratio of Mg to S in the Mg-S system is 2-5:1-10; the molar ratio of Mg to S in the MgS-S system is 2-5:1-10; the molar ratio of Mg to S in the MgSe-Se system is 2-5:1-10; the molar ratio of SrS to S in the SrS-S system is 2-5:1-10; the molar ratio of SrSe to Se in the SrSe-Se system is 2-5:1-10; the molar ratio of SrS to Ga2S3 in the SrS-Ga2S3 system is 1 -4:1-10; the molar ratio of SrSe to Ga2S3 in the SrSe-Ga2Se3 system is 1-4:1-10; the molar ratio of SrS, S to Ga2S3 in the SrS-S-Ga2S3 system is 2-5:1-10:1-3; the molar ratio of SrSe, Se to Ga2Se3 in the SrSe-Se-Ga2Se3 system is 2-5:1-10:1-3; the molar ratio of Ba to S in the Ba-S system is 2-5:1-6; the molar ratio of Ba to Se in the Ba-Se system is 2-5:1-6; the molar ratio of Ba to Ga2S3 in the Ba-Ga2S3 system is 2-5:1-6; the molar ratio of Ba to Ga2Se3 in the Ba-Ga2Se3 system is 2-5:1 -6; the molar ratio of Ba to MgS in the Ba-MgS system is 2-5:1-6; the molar ratio of Ba to MgSe in the Ba-MgSe system is 2-5:1-6; the molar ratio of BaS to MgS in the BaS-MgS system is 2-5:1-6; the molar ratio of BaSe to MgSe in the BaSe-MgSe system is 2-5:1-6; the molar ratio of BaS to S in the BaS-S system is 2-5:1-6; the molar ratio of BaSe to Se in the BaSe-Se system is 2-5:1-6; the molar ratio of BaS to Ga2S3 in the BaS-Ga2S3 system is 2-5:1-6; the molar ratio of BaSe to Ga2Se3 in the BaSe-Ga2Se3 system is 2-5:1-6;The molar ratio of Ba, Ga and S in the Ba-Ga-S system is 2-5:1-4:1-10; the molar ratio of Ba, Ga and Se in the Ba-Ga-Se system is 2-5:1-4:1-10; the molar ratio of Ba, S and Ga2S3 in the Ba-S-Ga2S3 system is 2-5:1-4:1-10; the molar ratio of Ba, S and Ga2S3 in the Ba-Se-Ga2Se3 system is 2-5:1-4:1-10; the molar ratio of BaS, S and MgS in the BaS-S-MgS system is 2-5:1-4:1-10; the molar ratio of BaSe, Se and The molar ratio of Pb to MgSe is 2-5:1-4:1-10; the molar ratio of Pb to S in the Pb-S system is 2-5:1-6; the molar ratio of Pb to Se in the Pb-Se system is 2-5:1-6; the molar ratio of Pb to Ga2S3 in the Pb-Ga2Se3 system is 2-5:1-6; the molar ratio of Pb to Ga2Se3 in the Pb-MgS system is 2-5:1-6; the molar ratio of Pb to MgSe in the Pb-MgSe system is 2-5:1-6; the molar ratio of PbS to S in the PbS-S system is 2-5:1-6 ; The molar ratio of PbSe to Se in the PbSe-Se system is 2-5:1-6; the molar ratio of PbS to Ga2S3 in the PbS-Ga2S3 system is 2-5:1-6; the molar ratio of PbSe to Ga2Se3 in the PbSe-Ga2Se3 system is 2-5:1-6; the molar ratio of Pb, Ga and S in the Pb-Ga-S system is 2-5:1-4:1-10; the molar ratio of Pb, Ga and Se in the Pb-Ga-Se system is 2-5:1-4:1-10; the molar ratio of Pb, S and Ga2S3 in the Pb-S-Ga2S3 system is 2-5:1-4:1-10; The molar ratio of Pb, Se and Ga2Se3 in Se-Ga2Se3 system is 2-5:1-4:1-10; the molar ratio of PbS, S and Ga2S3 in PbS-S-Ga2S3 system is 2-5:1-4:1-10; the molar ratio of PbSe, Se and Ga2Se3 in PbSe-Se-Ga2Se3 system is 2-5:1-4:1-10; the molar ratio of PbS, S and MgS in PbS-S-MgS system is 2-5:1-4:1-10; the molar ratio of PbSe, Se and MgSe in PbSe-Se-MgeS system is 2-5:1-4:1-10. ; 8. The use of a series of alkaline earth metal magnesium-based chalcogenide and alkaline earth metal magnesium-based selenide nonlinear optical crystals according to claim 1, characterized in that: This series of alkaline earth metal magnesium-based chalcogenide and alkaline earth metal magnesium-based selenide nonlinear optical crystals are used to prepare frequency doubling generators, up-frequency converters, down-frequency converters or optical parametric oscillators.

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