Cesium Gallium Chlorosulfide and Cesium Gallium Chlorosulfide Infrared Nonlinear Optical Crystal, Preparation Method and Application

Abstract

The present invention relates to a compound cesium gallium chloro sulfide and an infrared nonlinear optical crystal of cesium gallium chloro sulfide, a preparation method and an application thereof. The molecular formula of the compound is Cs3Ga8S 13 Cl, with a molecular weight of 1408.72. Its structure belongs to the monoclinic system, and the space group is Cc . It is prepared by the flux method. The chemical formula of the crystal is Cs3Ga8S 13 Cl, with a molecular weight of 1408.72. It crystallizes in the monoclinic system, and the space group is Cc . The unit cell parameters are a = 10.0698(5) Å, b = 17.8139(8) Å, c = 14.6479(6) Å, α = 90°, β = 90.218(2)°, γ = 90°, V = 2627.56(20) Å 3 . The cesium gallium chloro sulfide infrared nonlinear optical crystal is prepared by the flux method and the Bridgman method in a sealed vacuum quartz tube. It has the advantages of high laser damage resistance, moderate nonlinear optical effect, wide transmission band, large hardness, good mechanical properties, not easy to break and deliquesce, easy to process and preserve, etc., and can be used to manufacture infrared nonlinear optical devices.

Description

Technical Field

[0001] The present invention relates to a compound cesium gallium sulfide chloride and an infrared nonlinear optical crystal of cesium gallium sulfide chloride, a preparation method and an application thereof, belonging to the field of infrared nonlinear optical crystals. Background Art

[0002] Nonlinear optical materials, as the core devices of all-solid-state lasers, have important application values in the field of frequency conversion technology. Traditional oxy-nonlinear optical crystals, such as KBe 2 BO 3 F 2 (KBBF), β-BaB 2 O 4 (β-BBO), LiB 3 O 5 (LBO), LiNbO 3 (LN), KH 2 PO 4 (KDP) and KTiO(PO 4 )(KTP) have excellent optical properties and are widely used in the ultraviolet-visible-near infrared band. However, due to their low nonlinear optical coefficients and narrow infrared cut-off edges, such crystal materials are not suitable for applications in the mid- and far-infrared bands. Commercially available infrared nonlinear optical crystal materials such as AgGaS 2 (AGS), AgGaSe 2 (AGSe) and ZnGeP 2 (ZGP) generally have large nonlinear optical coefficients and wide infrared cut-off edges. However, due to the intrinsic defects in these materials, such as narrow band gaps, low laser damage thresholds, inability to achieve type-I phase matching, or strong two-photon absorption at 1 μm, their applications in the field of modern laser technology are severely limited. Therefore, there is an urgent need to develop and design new infrared nonlinear optical crystal materials with wide band gaps and large frequency doubling effects. Summary of the Invention

[0003] The object of the present invention is to provide a compound cesium gallium sulfide chloride with the chemical formula Cs 3 Ga 8 S 13 Cl;

[0004] Another object of the present invention is to provide an infrared nonlinear optical crystal of cesium gallium sulfide chloride;

[0005] Another object of the present invention is to provide a preparation method of a cesium gallium sulfide chloride nonlinear optical crystal;

[0006] Another object of the present invention is to provide the use of a cesium gallium sulfide chloride nonlinear optical crystal.

[0007] A compound cesium gallium chlorosulfide according to the present invention, the molecular formula of the compound is Cs 3 Ga 8 S 13 Cl, with a molecular weight of 1408.72, its structure belongs to the monoclinic system, and the space group is Cc.

[0008] The preparation method of the compound cesium gallium chlorosulfide is carried out according to the following steps:

[0009] a. According to the molar ratio of the chemical formula Cs 3 Ga 8 S 13 Cl, Cs∶Ga∶S∶Cl = 3∶8∶13∶1, weigh the raw materials under argon conditions, mix them evenly with the flux; load the mixture into a quartz container and evacuate it to 10 -3 Pa for melting and sealing; the Cs raw material is Cs, Cs 2 S or CsCl; the Ga raw material is Ga, Ga 2 S 3 or GaCl 3 , and the sulfur raw material is S; the flux is CsCl, raw material∶flux = 1∶1 - 5;

[0010] b. Place the sealed sample in step a in a muffle furnace, heat it at a rate of 10 - 40 °C / h to 850 - 900 °C, keep it at a constant temperature for 20 - 30 h; then cool it to room temperature at a rate of 10 - 20 °C / h, take it out, put it into a mortar for pounding and grinding, and wash the flux with deionized water to obtain a powdery pure sample of cesium gallium chlorosulfide.

[0011] A cesium gallium chlorosulfide infrared nonlinear optical crystal, the chemical formula of the crystal is Cs 3 Ga 8 S 13 Cl, with a molecular weight of 1408.72, crystallizes in the monoclinic system, the space group is Cc, and the unit cell parameters are α = 90°, β = 90.218(2)°, γ = 90°,

[0012] The preparation method of the cesium gallium chlorosulfide infrared nonlinear optical crystal is prepared by the flux method and the Bridgman method:

[0013] The growth of the cesium gallium chlorosulfide infrared nonlinear optical crystal by the flux method is specifically carried out according to the following steps:

[0014] a. According to the chemical formula Cs 3 Ga 8 S 13The molar ratio of Cs∶Ga∶S∶Cl in CsGaSCl is 3∶8∶13∶1, which is mixed evenly with the flux; it is loaded into a quartz tube, and the quartz tube is evacuated to 10 -3 Pa by a vacuum pump and then melted and sealed, where the Cs source material is Cs, Cs 2 S or CsCl; the Ga source material is Ga, Ga 2 S 3 or GaCl 3 ; the flux is CsCl, and the ratio of raw material to flux is 1∶1 - 5;

[0015] b. Put the quartz tube in step a into a programmable temperature-controlled muffle furnace, and raise the temperature to 850 - 900

[0016] °C at a heating rate of 10 - 20 °C / h, hold for 20 - 30 h, and then cool to room temperature at a cooling rate of 4 - 6 °C / h to obtain the cesium gallium sulfide chloride infrared nonlinear optical crystal.

[0017] The growth of the cesium gallium sulfide chloride infrared nonlinear optical crystal by the Bridgman method is carried out according to the following specific steps:

[0018] a. According to the molar ratio of Cs 3 Ga 8 S 13 Cl in CsGaSCl, Cs∶Ga∶S∶Cl = 3∶8∶13∶1, is mixed evenly with the flux; it is loaded into a quartz tube, and the quartz tube is evacuated to 10 -3 Pa and then melted and sealed, where the Cs source material is Cs, Cs 2 S or CsCl; the Ga source material is Ga, Ga 2 S 3 or GaCl 3 ; the flux is CsCl, and the ratio of raw material to flux is 1∶1 - 5;

[0019] b. Put the quartz tube in step a into a programmable temperature-controlled Bridgman furnace, and raise the temperature to 900 - 950 °C at a heating rate of 20 - 30 °C / h and hold for 30 - 40 h;

[0020] c. Lower the quartz tube in step b vertically at a speed of 0.1 - 0.2 mm / h, and the crystal grows during the descent of the Bridgman furnace. The growth period is 10 - 40 days. After the growth is completed, the crystal needs to be continuously annealed in the Bridgman furnace and cooled to room temperature at a cooling rate of 20 - 40 °C / h to obtain the cesium gallium sulfide chloride infrared nonlinear optical crystal;

[0021] Or place the quartz tube in step b in the Bridgman furnace, and lower the furnace temperature from 900 - 950

[0022] Cool it from ℃ to room temperature to obtain the cesium gallium chloro-sulfide infrared nonlinear optical crystal.

[0023] Use of the cesium gallium chloro-sulfide infrared nonlinear optical crystal in the preparation of infrared all-solid-state lasers, infrared laser guidance radars, laser medical applications, or medium- and long-distance laser communications.

[0024] The compound cesium gallium chloro-sulfide, the cesium gallium chloro-sulfide infrared nonlinear optical crystal, and the preparation method and application thereof according to the present invention. The cesium gallium chloro-sulfide crystal is prepared according to the following chemical reaction formula:

[0025] (1) 2Cs + CsCl + 8Ga + 13S = Cs 3 Ga 8 S 13 Cl;

[0026] (2) 2Cs + CsCl + 4Ga 2 S 3 + S = Cs 3 Ga 8 S 13 Cl;

[0027] (3) 9Cs + GaCl 3 + 23Ga + 39S = 3Cs 3 Ga 8 S 13 Cl;

[0028] (4) 18Cs + 2GaCl 3 + 23Ga 2 S 3 + 9S = 6Cs 3 Ga 8 S 13 Cl;

[0029] (5) 9Cs 2 S + 2GaCl 3 + 46Ga + 69S = 6Cs 3 Ga 8 S 13 Cl;

[0030] (6) 9Cs 2 S + 2GaCl 3 + 23Ga 2 S 3 = 6Cs 3 Ga 8 S 13 Cl;

[0031] (7) CsCl + Cs 2 S + 8Ga + 12S = Cs 3 Ga 8 S13 Cl;

[0032] (8)CsCl + Cs 2 S + 4Ga 2 S 3 = Cs 3 Ga 8 S 13 Cl.

[0033] The cesium gallium sulfide chloride compound, cesium gallium sulfide chloride infrared nonlinear optical crystal, preparation method and application thereof according to the present invention can obtain a cesium gallium sulfide chloride infrared nonlinear optical crystal with a size larger than 1.94×1.44×0.14 mm by using the flux method or the Bridgman method. 3 By using a large-sized crucible and extending the growth period, a cesium gallium sulfide chloride infrared nonlinear optical crystal with a correspondingly larger size can be obtained.

[0034] According to the crystallographic data of the crystal, the crystal blank is oriented, the crystal is cut at the required angles, thickness and cross-sectional dimensions, and the light-passing surface of the crystal is polished, and then it can be used as a nonlinear optical device.

[0035] The application of the cesium gallium sulfide chloride infrared nonlinear optical crystal according to the present invention in the field of laser technology includes uses in preparing infrared band laser frequency conversion crystals, infrared lasers, infrared electro-optic devices, infrared communication devices or infrared laser guidance devices.

[0036] The cesium gallium sulfide chloride infrared nonlinear optical crystal optical device according to the present invention has a wide band gap (3.76 eV), a high laser damage threshold (8×AGS), and a suitable nonlinear optical effect (0.6×AGS). Brief Description of the Drawings

[0037] Figure 1 This is the crystal structure diagram of Cs 3 Ga 8 S 13 Cl, where a is the coordination environment of Cs and Ga atoms, b is the [Ga 5 S 13 chain, c is the [Ga 7 S 13 layer, d is the [Ga 8 S 13 Cl] structural framework, and e and f are the three-dimensional structure diagrams of Cs 3 Ga 8 S 13 Cl observed from the a and b directions respectively;

[0038] Figure 2 This is the crystal structure diagram of Cs 3 Ga 8 S 13Experimental band gap diagram of Cl;

[0039] Figure 3 For the Cs of the present invention 3 Ga 8 S 13 Relationship diagram between the second harmonic generation intensity of AGS and the powder particle size;

[0040] Figure 4 For the Cs of the present invention 3 Ga 8 S 13 Working principle diagram of the CsGaSCl crystal, where 1 is a laser, 2 is a convex lens, 3 is a CsGaSCl crystal, 4 is a prism, and 5 is a filter; The laser beam emitted by the laser 1 passes through the convex lens 2 and enters the CsGaSCl single crystal 3, and the generated output laser beam passes through the prism 4 and the filter 5, thereby obtaining the required laser beam. Detailed implementation mode

[0041] Any feature disclosed in this specification, unless specifically described, can be replaced by other equivalent or similar-purpose alternative features. Unless specifically described, each feature is only an example of a series of equivalent or similar features. The above is only for helping to understand the present invention and should not be regarded as a specific limitation to the present invention.

[0042] The present invention is described in detail through the following drawings and the following embodiments.

[0043] Example 1

[0044] Using the chemical reaction formula 2Cs + CsCl + 8Ga + 13S = Cs 3 Ga 8 S 13 Cl to prepare the compound Cs 3 Ga 8 S 13 Cl:

[0045] a. Weigh the Cs source materials as Cs and CsCl, the Ga source material as Ga, and the sulfur source material as S under argon conditions according to the reaction formula, mix them evenly, add the flux CsCl in a molar ratio of raw material:flux = 1:5 and mix evenly. Then load the mixture into a quartz container and evacuate it to 10 -3 Pa for melting and sealing;

[0046] b. Place the sealed sample in step a in a muffle furnace, heat it to 900 °C at a rate of 10 °C / h, keep it at a constant temperature for 30 h, cool it to room temperature at a rate of 20 °C / h, take it out, put it into a mortar for pounding, and wash the flux with deionized water to obtain a powdery pure sample of CsGaSCl.

[0047] Example 2

[0048] Using the chemical reaction formula 2Cs + CsCl + 4Ga 2 S 3 + S = Cs 3 Ga 8 S 13 Cl to prepare the compound Cs 3 Ga 8 S 13 Cl:

[0049] a. Weigh the Cs source materials as Cs and CsCl, the Ga source material as Ga 2 S 3 , and the sulfur source material as S, mix them evenly, add the flux CsCl in a molar ratio of raw material∶flux = 1∶4, mix evenly, load the mixture into a quartz container, and evacuate it to 10 -3 Pa for melting and sealing under vacuum conditions;

[0050] b. Place the sealed sample in step a in a muffle furnace, heat it to 890°C at a rate of 20°C / h, keep it at a constant temperature for 28 h, then cool it to room temperature at a rate of 18°C / h, take it out, put it in a mortar for crushing and grinding, wash the flux with deionized water to obtain a powdery pure sample of cesium gallium chloride sulfide.

[0051] Example 3

[0052] Using the chemical reaction formula 9Cs + GaCl 3 + 23Ga + 39S = 3Cs 3 Ga 8 S 13 Cl to prepare the compound Cs 3 Ga 8 S 13 Cl:

[0053] a. Weigh the Cs source materials as Cs, the Ga source materials as Ga and GaCl 3 , and the sulfur source material as S, mix them evenly, add the flux CsCl in a molar ratio of raw material∶flux = 1∶3, mix evenly, load the mixture into a quartz container, and evacuate it to 10 -3 Pa for melting and sealing under vacuum conditions;

[0054] b. Place the sealed sample in step a in a muffle furnace, heat it to 880°C at a rate of 30°C / h, keep it at a constant temperature for 26 h, then cool it to room temperature at a rate of 16°C / h, take it out, put it in a mortar for crushing and grinding, wash the flux with deionized water to obtain a powdery pure sample of cesium gallium chloride sulfide.

[0055] Example 4

[0056] Using the chemical reaction formula 18Cs + 2GaCl 3 + 23Ga 2 S 3 + 9S = 6Cs 3 Ga 8 S 13 Cl to prepare the compound Cs 3 Ga 8 S 13 Cl:

[0057] a. Weigh the Cs source material as Cs, the Ga source material as Ga 2 S 3 and GaCl 3 , and the sulfur source material as S, mix them evenly, add the flux CsCl in a molar ratio of raw material:flux = 1:2, mix evenly, load the mixture into a quartz container, and evacuate it to 10 -3 Pa for melting and sealing;

[0058] b. Place the sealed sample in step a in a muffle furnace, heat it to 870°C at a rate of 40°C / h, keep it at a constant temperature for 24 h, then cool it to room temperature at a rate of 14°C / h, take it out, put it in a mortar for crushing and grinding, wash the flux with deionized water to obtain a powdery pure sample of cesium gallium chlorosulfide.

[0059] Example 5

[0060] Using the chemical reaction formula 9Cs 2 S + 2GaCl 3 + 46Ga + 69S = 6Cs 3 Ga 8 S 13 Cl to prepare the compound Cs 3 Ga 8 S 13 Cl:

[0061] a. Weigh the Cs source material as Cs 2 S, the Ga source material as Ga and GaCl 3 , and the sulfur source material as S, mix them evenly, add the flux CsCl in a molar ratio of raw material:flux = 1:1, mix evenly, load the mixture into a quartz container, and evacuate it to 10 -3 Pa for melting and sealing;

[0062] b. Place the sealed sample in step a in a muffle furnace, heat it to 860°C at a rate of 40°C / h, keep it at a constant temperature for 22 h, then cool it to room temperature at a rate of 12°C / h, take it out, put it in a mortar for crushing and grinding, wash the flux with deionized water to obtain a powdery pure sample of cesium gallium chlorosulfide.

[0063] Example 6

[0064] Using the chemical reaction formula 9Cs 2 S + 2GaCl 3 + 23Ga 2 S 3 = 6Cs 3 Ga 8 S 13 Cl to prepare the compound Cs 3 Ga 8 S 13 Cl:

[0065] a. Weigh the Cs source material as Cs 2 S, the Ga source material as Ga 2 S 3 and GaCl 3 , and the sulfur source material as S and mix them evenly. Add the flux CsCl according to the molar ratio of raw material:flux = 1:3 and mix evenly. Then load the mixture into a quartz container and evacuate it to 10 -3 Pa for melting and sealing;

[0066] b. Place the sealed sample in step a in a muffle furnace, heat it to 850°C at a rate of 40°C / h, keep it at a constant temperature for 20 h, then cool it to room temperature at a rate of 10°C / h, take it out, put it in a mortar and pestle for pounding and grinding, and wash the flux with deionized water to obtain a powdery pure sample of cesium gallium chlorosulfide.

[0067] Example 7

[0068] Using the chemical reaction formula CsCl + Cs 2 S + 8Ga + 12S = Cs 3 Ga 8 S 13 Cl to prepare the compound Cs 3 Ga 8 S 13 Cl:

[0069] a. Weigh the Cs source materials as Cs 2 S and CsCl, the Ga source material as Ga, and the sulfur source material as S and mix them evenly. Add the flux CsCl according to the molar ratio of raw material:flux = 1:4 and mix evenly. Then load the mixture into a quartz container and evacuate it to 10 -3 Pa for melting and sealing;

[0070] b. Place the sealed sample in step a in a muffle furnace, heat it to 870 °C at a rate of 30 °C / h, keep it at a constant temperature for 22 h, then cool it to room temperature at a rate of 12 °C / h, take it out, put it in a mortar for crushing and grinding, and wash the flux with deionized water to obtain a powdery pure sample of cesium gallium sulfide chloride.

[0071] Example 8

[0072] Using the chemical reaction formula CsCl + Cs 2 S + 4Ga 2 S 3 = Cs 3 Ga 8 S 13 Cl to prepare the compound Cs 3 Ga 8 S 13 Cl:

[0073] a. Weigh the Cs source material as Cs 2 S and CsCl, the Ga source material as Ga 2 S 3 , and the sulfur source material as S, mix them evenly, add the flux CsCl in a molar ratio of raw material:flux = 1:5, mix evenly, then load the mixture into a quartz container, and evacuate it to 10 -3 Pa for melting and sealing;

[0074] b. Place the sealed sample in step a in a muffle furnace, heat it to 900 °C at a rate of 20 °C / h, keep it at a constant temperature for 30 h, then cool it to room temperature at a rate of 16 °C / h, take it out, put it in a mortar for crushing and grinding, and wash the flux with deionized water to obtain a powdery pure sample of cesium gallium sulfide chloride.

[0075] Example 9

[0076] Growth of cesium gallium sulfide chloride infrared nonlinear optical crystal by flux method:

[0077] Using the chemical reaction formula 2Cs + CsCl + 8Ga + 13S = Cs 3 Ga 8 S 13 Cl to prepare cesium gallium sulfide chloride infrared nonlinear optical crystal:

[0078] a. Weigh 0.566 g of Cs, 0.359 g of CsCl, 1.188 g of Ga, and 0.888 g of S under argon conditions according to the molar ratio of 2:1:8:13, and then weigh 3 g of the flux CsCl with a raw material:flux ratio of 1:1, mix them evenly, load them into a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to evacuate the quartz tube to 10 -3 Pa vacuum and then carry out melting and sealing;

[0079] b. Place the quartz tube in step a into a programmable temperature-controlled muffle furnace, raise the temperature to 850 °C at a heating rate of 10 °C / h, hold for 20 h, and then cool to room temperature at a cooling rate of 4 °C / h to obtain a chlorothioindate cesium infrared nonlinear optical crystal with dimensions of 2.00×1.50×0.14 mm 3

[0080] Example 10

[0081] Growth of chlorothioindate cesium infrared nonlinear optical crystal by flux method:

[0082] Using the chemical reaction formula 2Cs + CsCl + 4Ga 2 S 3 + S = Cs 3 Ga 8 S 13 Cl to prepare chlorothioindate cesium infrared nonlinear optical crystal:

[0083] a. Weigh 0.566 g of Cs, 0.359 g of CsCl, 2.007 g of Ga 2 S 3 and 0.068 g of S in an argon atmosphere according to a molar ratio of 2:1:4:1, and then weigh 6 g of the flux CsCl according to a raw material:flux = 1:2. Mix them evenly, put them into a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to evacuate the quartz tube to a vacuum degree of 10 -3 Pa and then carry out melting and sealing;

[0084] b. Place the quartz tube in step a into a programmable temperature-controlled muffle furnace, raise the temperature to 860 °C at a heating rate of 12 °C / h, hold for 22 h, and then cool to room temperature at a cooling rate of 4.5 °C / h to obtain a chlorothioindate cesium infrared nonlinear optical crystal with dimensions of 1.98×1.48×0.16 mm 3

[0085] Example 11

[0086] Growth of chlorothioindate cesium infrared nonlinear optical crystal by flux method:

[0087] Using the chemical reaction formula 9Cs + GaCl 3 + 23Ga + 39S = 3Cs 3 Ga 8 S 13 Cl to prepare chlorothioindate cesium infrared nonlinear optical crystal:

[0088] a. Weigh 0.849 g of Cs, 0.125 g of GaCl 3 ​​, 1.138 g of Ga and 0.888 g of S, and then weigh 9 g of the flux CsCl with the raw material:flux = 1:3, mix evenly, put it into a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the quartz tube to 10 -3 Pa vacuum and then carry out melting and sealing;

[0089] b. Put the quartz tube in step a into a programmable temperature-controlled muffle furnace, raise the temperature to 870 °C at a heating rate of 14 °C / h, keep it warm for 24 h, and then cool it to room temperature at a cooling rate of 5 °C / h to obtain a chloro-thio-gallium-caesium infrared nonlinear optical crystal with dimensions of 1.96×1.46×0.18 mm 3 of chloro-thio-gallium-caesium infrared nonlinear optical crystal.

[0090] Example 12

[0091] Growth of chloro-thio-gallium-caesium infrared nonlinear optical crystal by the flux method:

[0092] Using the chemical reaction formula 18Cs + 2GaCl 3 + 23Ga 2 S 3 + 9S = 6Cs 3 Ga 8 S 13 Cl to prepare chloro-thio-gallium-caesium infrared nonlinear optical crystal:

[0093] a. Weigh 0.849 g of Cs, 0.125 g of GaCl 3 , 1.924 g of Ga 2 S 3 and 0.102 g of S under argon atmosphere according to the molar ratio of 18:2:23:9, and then weigh 12 g of the flux CsCl with the raw material:flux = 1:4, mix evenly, put it into a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the quartz tube to 10 -3 Pa vacuum and then carry out melting and sealing;

[0094] b. Put the quartz tube in step a into a programmable temperature-controlled muffle furnace, raise the temperature to 880 °C at a heating rate of 16 °C / h, keep it warm for 26 h, and then cool it to room temperature at a cooling rate of 5.5 °C / h to obtain a chloro-thio-gallium-caesium infrared nonlinear optical crystal with dimensions of 1.94×1.44×0.20 mm 3 of chloro-thio-gallium-caesium infrared nonlinear optical crystal.

[0095] Example 13

[0096] Growth of chloro-thio-gallium-caesium infrared nonlinear optical crystal by the flux method:

[0097] Using the chemical reaction formula 9Cs 2 S + 2GaCl 3 + 46Ga + 69S = 6Cs3 Ga 8 S 13 Preparation of cesium chloro-thio-gallate infrared nonlinear optical crystal:

[0098] a. Weigh 0.952 g of Cs 2 S, 0.125 g of GaCl 3 , 1.138 g of Ga and 0.785 g of S according to the molar ratio of 9:2:46:69 under argon atmosphere. Then, weigh 15 g of flux CsCl with the ratio of raw material:flux = 1:5, mix them evenly, put them into a quartz tube with a length of 24 cm and a diameter of 12 mm, and evacuate the quartz tube to a vacuum degree of 10 -3 Pa by a vacuum pump and then carry out melting and sealing;

[0099] b. Put the quartz tube in step a into a programmable temperature-controlled muffle furnace, heat it to 890 °C at a heating rate of 18 °C / h, keep it warm for 28 h, and then cool it to room temperature at a cooling rate of 6 °C / h to obtain a cesium chloro-thio-gallate infrared nonlinear optical crystal with dimensions of 2.02×1.48×0.16 mm 3

[0100] Example 14

[0101] Growth of cesium chloro-thio-gallate infrared nonlinear optical crystal by flux method:

[0102] Using the chemical reaction formula 9Cs 2 S + 2GaCl 3 + 23Ga 2 S 3 = 6Cs 3 Ga 8 S 13 Cl to prepare cesium chloro-thio-gallate infrared nonlinear optical crystal:

[0103] a. Weigh 0.951 g of Cs 2 S, 0.125 g of GaCl 3 and 1.924 g of Ga 2 S 3 , then weigh 12 g of flux CsCl with the ratio of raw material:flux = 1:4, mix them evenly, put them into a quartz tube with a length of 24 cm and a diameter of 12 mm, and evacuate the quartz tube to a vacuum degree of 10 -3 Pa by a vacuum pump and then carry out melting and sealing;

[0104] b. Put the quartz tube in step a into a programmable temperature-controlled muffle furnace, heat it to 900 °C at a heating rate of 20 °C / h, keep it warm for 30 h, and then cool it to room temperature at a cooling rate of 5 °C / h to obtain a cesium chloro-thio-gallate infrared nonlinear optical crystal with dimensions of 2.04×1.46×0.18 mm 3 ​Cesium chloro-thio-gallate infrared nonlinear optical crystal.

[0105] Example 15

[0106] Growth of cesium chloro-thio-gallate infrared nonlinear optical crystal by flux method:

[0107] Using the chemical reaction formula CsCl + Cs 2 S + 8Ga + 12S = Cs 3 Ga 8 S 13 Cl to prepare cesium chloro-thio-gallate infrared nonlinear optical crystal:

[0108] a. Weigh 0.359 g of CsCl, 0.634 g of Cs 2 S, 1.188 g of Ga and 0.819 g of S according to the molar ratio of 1:1:8:12 under argon atmosphere. Then weigh 9 g of flux CsCl with the ratio of raw material:flux = 1:3, mix them evenly, put them into a quartz tube with a length of 24 cm and a diameter of 12 mm, and evacuate the quartz tube to a vacuum degree of 10 -3 Pa and then carry out melting and sealing;

[0109] b. Put the quartz tube in step a into a programmable temperature-controlled muffle furnace, heat it to 890 °C at a heating rate of 14 °C / h, keep it for 22 h, and then cool it to room temperature at a cooling rate of 4.5 °C / h to obtain cesium chloro-thio-gallate infrared nonlinear optical crystal with a size of 2.06×1.44×0.14 mm 3

[0110] Example 16

[0111] Growth of cesium chloro-thio-gallate infrared nonlinear optical crystal by flux method:

[0112] Using the chemical reaction formula CsCl + Cs 2 S + 4Ga 2 S 3 = Cs 3 Ga 8 S 13 Cl to prepare cesium chloro-thio-gallate infrared nonlinear optical crystal:

[0113] a. Weigh 0.359 g of CsCl, 0.634 g of Cs 2 S and 2.007 g of Ga 2 S 3 according to the molar ratio of 1:1:4 under argon atmosphere. Then weigh 6 g of flux CsCl with the ratio of raw material:flux = 1:2, mix them evenly, put them into a quartz tube with a length of 24 cm and a diameter of 12 mm, and evacuate the quartz tube to a vacuum degree of 10 -3 Pa and then carry out melting and sealing;

[0114] b. Place the quartz tube in step a into a programmable temperature-controlled muffle furnace, raise the temperature to 880 °C at a heating rate of 10 °C / h, hold for 20 h, and then cool to room temperature at a cooling rate of 4 °C / h to obtain a cesium gallium chloro-sulfide infrared nonlinear optical crystal with dimensions of 2.00×1.50×0.20 mm 3

[0115] Example 17

[0116] To grow a cesium gallium chloro-sulfide infrared nonlinear optical crystal by the Bridgman method, the specific operation is carried out according to the following steps:

[0117] a. Weigh 0.566 g of Cs, 0.359 g of CsCl, 1.188 g of Ga, and 0.888 g of S under argon conditions according to a molar ratio of 2:1:8:13. Then, weigh 3 g of flux according to a raw material:flux = 1:1, mix it evenly with the raw materials, place it into a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then perform melting and sealing;

[0118] b. Place the quartz tube in step a into a programmable temperature-controlled Bridgman furnace, raise the temperature to 900 °C at a heating rate of 20 °C / h, and hold for 30 h;

[0119] c. Vertically lower the quartz tube in step b at a speed of 0.10 mm / h, and the crystal grows during the descent of the Bridgman furnace. The growth period is 10 days. After the growth is completed, continuously anneal the crystal in the Bridgman furnace and cool it to room temperature at a cooling rate of 40 °C / h to obtain a cesium gallium chloro-sulfide infrared nonlinear optical crystal with dimensions of 2.06×1.44×0.20 mm 3

[0120] Example 18

[0121] To grow a cesium gallium chloro-sulfide infrared nonlinear optical crystal by the Bridgman method, the specific operation is carried out according to the following steps:

[0122] a. Weigh 0.566 g of Cs, 0.359 g of CsCl, 1.188 g of Ga, and 0.888 g of S under argon conditions according to a molar ratio of 2:1:8:13. Then, weigh 3 g of flux according to a raw material:flux = 1:1, mix it evenly with the raw materials, place it into a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then perform melting and sealing;

[0123] b. Place the quartz tube in step a into a programmable temperature-controlled Bridgman furnace, raise the temperature to 900 °C at a heating rate of 20 °C / h, and hold for 30 h;

[0124] ​​c. Place the quartz tube in step b in a crucible descent furnace, and lower the furnace temperature from 900 °C to room temperature at a rate of 1.0 °C / h to obtain a CsGaS₂Cl infrared nonlinear optical crystal with dimensions of 2.04×1.46×0.22 mm. 3 of the CsGaS₂Cl infrared nonlinear optical crystal.

[0125] Example 19

[0126] The CsGaS₂Cl infrared nonlinear optical crystal was grown by the Bridgman method. The specific operations were carried out according to the following steps:

[0127] a. Weigh 0.566 g of Cs, 0.359 g of CsCl, 2.007 g of Ga 2 S 3 and 0.068 g of S according to the molar ratio of 2:1:4:1 under argon atmosphere. Then, weigh 6 g of flux according to the ratio of raw material:flux = 1:2, mix it evenly with the raw materials, place it in a quartz tube with a length of 24 cm and a diameter of 12 mm, and evacuate the air pressure in the quartz tube to 10 -3 Pa and then conduct melting and sealing.

[0128] b. Place the quartz tube in step a in a programmable temperature-controlled crucible descent furnace, heat it to 910 °C at a rate of 22 °C / h, and keep it at this temperature for 32 h.

[0129] c. Lower the quartz tube in step b vertically at a speed of 0.12 mm / h, and the crystal grows during the descent of the crucible in the furnace. The growth cycle is 15 days. After the growth is completed, anneal the crystal continuously in the crucible descent furnace and cool it to room temperature at a rate of 35 °C / h to obtain a CsGaS₂Cl infrared nonlinear optical crystal with dimensions of 2.04×1.46×0.18 mm. 3 of the CsGaS₂Cl infrared nonlinear optical crystal.

[0130] Example 20

[0131] The CsGaS₂Cl infrared nonlinear optical crystal was grown by the Bridgman method. The specific operations were carried out according to the following steps:

[0132] a. Weigh 0.566 g of Cs, 0.359 g of CsCl, 2.007 g of Ga 2 S 3 and 0.068 g of S according to the molar ratio of 2:1:4:1 under argon atmosphere. Then, weigh 6 g of flux according to the ratio of raw material:flux = 1:2, mix it evenly with the raw materials, place it in a quartz tube with a length of 24 cm and a diameter of 12 mm, and evacuate the air pressure in the quartz tube to 10 -3 Pa and then conduct melting and sealing.

[0133] b. Place the quartz tube in step a in a programmable temperature-controlled crucible descent furnace, heat it to 910 °C at a rate of 22 °C / h, and keep it at this temperature for 32 h.

[0134] c. Place the quartz tube in step b in a crucible lowering furnace, and lower the furnace temperature from 910 °C to room temperature at a cooling rate of 1.0 °C / h to obtain a cesium gallium chloro-sulfide infrared nonlinear optical crystal with dimensions of 2.02×1.44×0.16 mm 3

[0135] Example 21

[0136] To grow a cesium gallium chloro-sulfide infrared nonlinear optical crystal by the crucible lowering method, the specific operation is carried out according to the following steps:

[0137] a. Weigh 0.849 g of Cs, 0.125 g of GaCl 3 , 1.138 g of Ga and 0.888 g of S under argon conditions according to a molar ratio of 9:1:23:39. Then, weigh 9 g of the flux CsCl with a raw material:flux ratio of 1:3, mix it evenly with the raw materials, place it in a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then carry out melting and sealing;

[0138] b. Place the quartz tube in step a in a crucible lowering furnace with programmable temperature control, raise the temperature to 920 °C at a heating rate of 24 °C / h, and hold for 34 h;

[0139] c. Lower the quartz tube in step b vertically at a speed of 0.14 mm / h, and the crystal grows during the descent of the crucible lowering furnace. The growth period is 20 days. After the growth is completed, the crystal needs to be continuously annealed in the crucible lowering furnace and cooled to room temperature at a cooling rate of 30 °C / h to obtain a cesium gallium chloro-sulfide infrared nonlinear optical crystal with dimensions of 2.04×1.48×0.16 mm 3

[0140] Example 22

[0141] To grow a cesium gallium chloro-sulfide infrared nonlinear optical crystal by the crucible lowering method, the specific operation is carried out according to the following steps:

[0142] a. Weigh 0.849 g of Cs, 0.125 g of GaCl 3 , 1.138 g of Ga and 0.888 g of S under argon conditions according to a molar ratio of 9:1:23:39. Then, weigh 9 g of the flux CsCl with a raw material:flux ratio of 1:3, mix it evenly with the raw materials, place it in a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then carry out melting and sealing;

[0143] ​​b. Place the quartz tube in step a into a crucible lowering furnace with programmable temperature control, heat it to 920 °C at a heating rate of 24 °C / h, and hold for 34 h;

[0144] c. Place the quartz tube in step b in the crucible lowering furnace, and lower the furnace temperature from 920 °C to room temperature at a cooling rate of 2.0 °C / h to obtain a cesium gallium chloro-sulfide infrared nonlinear optical crystal with dimensions of 2.02×1.46×0.14 mm 3

[0145] Example 23

[0146] To grow a cesium gallium chloro-sulfide infrared nonlinear optical crystal by the Bridgman method, the specific operation is carried out according to the following steps:

[0147] a. Weigh 0.849 g of Cs, 0.125 g of GaCl 3 , 1.924 g of Ga 2 S 3 and 0.102 g of S in an argon atmosphere according to a molar ratio of 18:2:23:9. Then, weigh 12 g of the flux CsCl with a raw material:flux ratio of 1:4, mix it evenly with the raw materials, place it in a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then perform melting and sealing;

[0148] b. Place the quartz tube in step a into a crucible lowering furnace with programmable temperature control, heat it to 930 °C at a heating rate of 26 °C / h, and hold for 36 h;

[0149] c. Lower the quartz tube in step b vertically at a speed of 0.16 mm / h, and the crystal grows during the descent of the crucible lowering furnace. The growth period is 25 days. After the growth is completed, the crystal needs to be continuously annealed in the crucible lowering furnace and cooled to room temperature at a cooling rate of 25 °C / h to obtain a cesium gallium chloro-sulfide infrared nonlinear optical crystal with dimensions of 2.02×1.46×0.18 mm 3

[0150] Example 24

[0151] To grow a cesium gallium chloro-sulfide infrared nonlinear optical crystal by the Bridgman method, the specific operation is carried out according to the following steps:

[0152] a. Weigh 0.849 g of Cs, 0.125 g of GaCl 3 , 1.924 g of Ga 2 S 3and 0.102 g of S, and then weigh 12 g of the flux CsCl with a raw material:flux ratio of 1:4, mix it evenly with the raw materials, place it in a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then carry out melting and sealing;

[0153] b. Put the quartz tube in step a into a crucible lowering furnace with programmable temperature control, raise the temperature to 930 °C at a heating rate of 26 °C / h, and keep it warm for 36 h;

[0154] c. Place the quartz tube in step b in the crucible lowering furnace, and lower the furnace temperature from 930 °C to room temperature at a cooling rate of 1.5 °C / h to obtain a cesium chloro-thiogallate infrared nonlinear optical crystal with dimensions of 2.04×1.48×0.20 mm 3

[0155] Example 25

[0156] To grow a cesium chloro-thiogallate infrared nonlinear optical crystal by the Bridgman method, the specific operation is carried out according to the following steps:

[0157] a. Weigh 0.952 g of Cs 2 S, 0.125 g of GaCl 3 , 1.138 g of Ga and 0.785 g of S under argon conditions according to a molar ratio of 9:2:46:69, and then weigh 15 g of the flux CsCl with a raw material:flux ratio of 1:5, mix it evenly with the raw materials, place it in a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then carry out melting and sealing;

[0158] b. Put the quartz tube in step a into a crucible lowering furnace with programmable temperature control, raise the temperature to 940 °C at a heating rate of 28 °C / h, and keep it warm for 38 h;

[0159] c. Vertically lower the quartz tube in step b at a speed of 0.18 mm / h, and the crystal grows during the descent of the crucible lowering furnace. The growth period is 30 days. After the growth is completed, continuously anneal the crystal in the crucible lowering furnace and lower the temperature to room temperature at a cooling rate of 23 °C / h to obtain a cesium chloro-thiogallate infrared nonlinear optical crystal with dimensions of 2.00×1.44×0.20 mm 3

[0160] Example 26

[0161] To grow a cesium chloro-thiogallate infrared nonlinear optical crystal by the Bridgman method, the specific operation is carried out according to the following steps:

[0162] a. Weigh 0.952 g of Cs​​2 S, 0.125 g of GaCl 3 , 1.138 g of Ga and 0.785 g of S, and then 15 g of flux CsCl was weighed according to the ratio of raw material:flux = 1:5, mixed evenly with the raw materials, placed in a quartz tube with a length of 24 cm and a diameter of 12 mm, and the air pressure in the quartz tube was pumped to 10 -3 Pa and then melt-sealed;

[0163] b. The quartz tube in step a was placed in a programmed temperature-controlled crucible drop furnace, heated to 940 °C at a heating rate of 28 °C / h, and held for 38 h;

[0164] c. The quartz tube in step b was placed in the crucible drop furnace, and the furnace temperature was decreased from 940 °C to room temperature at a cooling rate of 2.0 °C / h to obtain a cesium gallium chloro-sulfide infrared nonlinear optical crystal with dimensions of 2.02×1.42×0.22 mm 3 .

[0165] Example 27

[0166] The cesium gallium chloro-sulfide infrared nonlinear optical crystal was grown by the crucible drop method, and the specific operation was carried out according to the following steps:

[0167] a. 0.951 g of Cs 2 S, 0.125 g of GaCl 3 and 1.924 g of Ga 2 S 3 were weighed under argon according to the molar ratio of 9:2:23, and then 12 g of flux CsCl was weighed according to the ratio of raw material:flux = 1:4, mixed evenly with the raw materials, placed in a quartz tube with a length of 24 cm and a diameter of 12 mm, and the air pressure in the quartz tube was pumped to 10 -3 Pa and then melt-sealed;

[0168] b. The quartz tube in step a was placed in a programmed temperature-controlled crucible drop furnace, heated to 950 °C at a heating rate of 30 °C / h, and held for 40 h;

[0169] c. The quartz tube in step b was vertically lowered at a speed of 0.20 mm / h, and the crystal was grown during the descent of the crucible drop furnace. The growth period was 35 days. After the growth was completed, the crystal was continuously annealed in the crucible drop furnace and cooled to room temperature at a cooling rate of 20 °C / h to obtain a cesium gallium chloro-sulfide infrared nonlinear optical crystal with dimensions of 1.98×1.46×0.18 mm 3 .

[0170] Example 28

[0171] The cesium gallium chloro-sulfide infrared nonlinear optical crystal was grown by the crucible drop method, and the specific operation was carried out according to the following steps:

[0172] a. Weigh 0.951 g of Cs, 0.125 g of GaCl, and 1.924 g of GaS according to a molar ratio of 9:2:23 under argon atmosphere. Then, weigh 12 g of CsCl as the flux according to a raw material:flux ratio of 1:4, mix it evenly with the raw materials, place them in a quartz tube with a length of 24 cm and a diameter of 12 mm, and evacuate the air pressure in the quartz tube to 10 Pa using a vacuum pump, and then perform melting and sealing. 2 S, 0.125 g of GaCl 3 and 1.924 g of Ga 2 S 3 , and then weigh 12 g of the flux CsCl according to the ratio of raw material:flux = 1:4, mix it evenly with the raw materials, place it in a quartz tube with a length of 24 cm and a diameter of 12 mm, and evacuate the air pressure in the quartz tube to 10 Pa using a vacuum pump, and then perform melting and sealing; -3 Pa and then perform melting and sealing;

[0173] b. Place the quartz tube in step a into a temperature-programmed crucible descent furnace, heat it to 950 °C at a heating rate of 30 °C / h, and hold for 40 h;

[0174] c. Place the quartz tube in step b in the crucible descent furnace, and lower the furnace temperature from 950 °C to room temperature at a cooling rate of 1.5 °C / h to obtain a cesium gallium sulfide chloride infrared nonlinear optical crystal with dimensions of 2.00×1.48×0.16 mm. 3 of cesium gallium sulfide chloride infrared nonlinear optical crystal.

[0175] Example 29

[0176] To grow a cesium gallium sulfide chloride infrared nonlinear optical crystal by the crucible descent method, the specific operations are carried out according to the following steps:

[0177] a. Weigh 0.359 g of CsCl, 0.634 g of CsS, 1.188 g of Ga, and 0.819 g of S according to a molar ratio of 1:1:8:12 under argon atmosphere. Then, weigh 9 g of the flux CsCl according to the ratio of raw material:flux = 1:3, mix it evenly with the raw materials, place it in a quartz tube with a length of 24 cm and a diameter of 12 mm, and evacuate the air pressure in the quartz tube to 10 Pa using a vacuum pump, and then perform melting and sealing; 2 S, 1.188 g of Ga and 0.819 g of S, and then weigh 9 g of the flux CsCl according to the ratio of raw material:flux = 1:3, mix it evenly with the raw materials, place it in a quartz tube with a length of 24 cm and a diameter of 12 mm, and evacuate the air pressure in the quartz tube to 10 Pa using a vacuum pump, and then perform melting and sealing; -3 Pa and then perform melting and sealing;

[0178] b. Place the quartz tube in step a into a temperature-programmed crucible descent furnace, heat it to 920 °C at a heating rate of 26 °C / h, and hold for 36 h;

[0179] c. Lower the quartz tube in step b vertically at a speed of 0.12 mm / h, and the crystal grows during the descent of the crucible in the crucible descent furnace. The growth period is 40 days. After the growth is completed, the crystal is continuously annealed in the crucible descent furnace and cooled to room temperature at a cooling rate of 35 °C / h to obtain a cesium gallium sulfide chloride infrared nonlinear optical crystal with dimensions of 1.96×1.48×0.16 mm. 3 of cesium gallium sulfide chloride infrared nonlinear optical crystal.

[0180] Example 30

[0181] The cesium chloro-thio-gallate infrared nonlinear optical crystal is grown by the Bridgman method, and the specific operation is carried out according to the following steps:

[0182] a. Weigh 0.359 g of CsCl, 0.634 g of Cs 2 S, 1.188 g of Ga and 0.819 g of S according to the molar ratio of 1:1:8:12 under argon atmosphere. Then, weigh 9 g of the flux CsCl with the raw materials:flux = 1:3, mix them evenly, place them in a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then carry out melting and sealing;

[0183] b. Put the quartz tube in step a into a Bridgman furnace with programmable temperature control, heat it to 920 °C at a heating rate of 26 °C / h, and keep it at this temperature for 36 h;

[0184] c. Place the quartz tube in step b in the Bridgman furnace, and lower the furnace temperature from 920 °C to room temperature at a cooling rate of 2.0 °C / h to obtain a cesium chloro-thio-gallate infrared nonlinear optical crystal with dimensions of 1.98×1.46×0.14 mm 3

[0185] Example 31

[0186] The cesium chloro-thio-gallate infrared nonlinear optical crystal is grown by the Bridgman method, and the specific operation is carried out according to the following steps:

[0187] a. Weigh 0.359 g of CsCl, 0.634 g of Cs 2 S and 2.007 g of Ga 2 S 3 according to the molar ratio of 1:1:4 under argon atmosphere. Then, weigh 6 g of the flux CsCl with the raw materials:flux = 1:2, mix them evenly, place them in a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then carry out melting and sealing;

[0188] b. Put the quartz tube in step b into a Bridgman furnace with programmable temperature control, heat it to 900 °C at a heating rate of 22 °C / h, and keep it at this temperature for 38 h;

[0189] c. Lower the quartz tube in step b vertically at a speed of 0.18 mm / h, and the crystal grows during the descent of the Bridgman furnace. The growth period is 20 days. After the growth is completed, the crystal is continuously annealed in the Bridgman furnace and cooled to room temperature at a cooling rate of 23 °C / h to obtain a cesium chloro-thio-gallate infrared nonlinear optical crystal with dimensions of 1.94×1.50×0.14 mm 3

[0190] Example 32​​

[0191] The cesium chloro-thio-gallate infrared nonlinear optical crystal is grown by the Bridgman method, and the specific operation is carried out according to the following steps:

[0192] a. Weigh 0.359 g of CsCl, 0.634 g of Cs 2 S and 2.007 g of Ga 2 S 3 in an argon atmosphere according to a molar ratio of 1:1:4, and then weigh 6 g of the flux CsCl according to a raw material:flux ratio of 1:2, mix it evenly with the raw materials, place it in a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then carry out melting and sealing;

[0193] b. Place the quartz tube in step b into a Bridgman furnace with programmable temperature control, heat it to 900 °C at a heating rate of 22 °C / h, and keep it at this temperature for 38 h;

[0194] c. Place the quartz tube in step b in the Bridgman furnace, and cool the furnace temperature from 900 °C to room temperature at a cooling rate of 1.5 °C / h to obtain a cesium chloro-thio-gallate infrared nonlinear optical crystal with dimensions of 1.96×1.48×0.16 mm 3 .

[0195] Example 33

[0196] The cesium chloro-thio-gallate infrared nonlinear optical crystal is grown by the Bridgman method, and the specific operation is carried out according to the following steps:

[0197] a. Weigh 0.566 g of Cs, 0.359 g of CsCl, 1.188 g of Ga and 0.888 g of S in an argon atmosphere according to a molar ratio of 2:1:8:13, and then weigh 3 g of the flux CsCl according to a raw material:flux ratio of 1:1, mix it evenly with the raw materials, place it in a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then carry out melting and sealing;

[0198] b. Place the quartz tube in step a into a Bridgman furnace with programmable temperature control, heat it to 900 °C at a heating rate of 28 °C / h, and keep it at this temperature for 40 h;

[0199] c. Lower the quartz tube in step b vertically at a speed of 0.20 mm / h, and the crystal grows during the descent of the Bridgman furnace. The growth period is 10 days. After the growth is completed, the crystal is continuously annealed in the Bridgman furnace and cooled to room temperature at a cooling rate of 40 °C / h to obtain a cesium chloro-thio-gallate infrared nonlinear optical crystal with dimensions of 1.94×1.50×0.12 mm 3 .

[0200] Example 34

[0201] The cesium gallium sulfide chloride infrared nonlinear optical crystal is grown by the Bridgman method. The specific operation is carried out according to the following steps:

[0202] a. Weigh 0.566 g of Cs, 0.359 g of CsCl, 1.188 g of Ga, and 0.888 g of S according to the molar ratio of 2:1:8:13 under argon atmosphere. Then, weigh 3 g of the flux CsCl with the ratio of raw material:flux = 1:1, mix it evenly with the raw materials, place them in a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then carry out melting and sealing;

[0203] b. Put the quartz tube in step a into a Bridgman furnace with programmable temperature control, heat it to 900 °C at a heating rate of 28 °C / h, and keep it at this temperature for 40 h;

[0204] c. Place the quartz tube in step b in the Bridgman furnace, and lower the furnace temperature from 900 °C to room temperature at a cooling rate of 2.0 °C / h to obtain a cesium gallium sulfide chloride infrared nonlinear optical crystal with dimensions of 1.96×1.48×0.18 mm 3 .

[0205] Example 35

[0206] The cesium gallium sulfide chloride infrared nonlinear optical crystal is grown by the Bridgman method. The specific operation is carried out according to the following steps:

[0207] a. Weigh 0.566 g of Cs, 0.359 g of CsCl, 2.007 g of Ga 2 S 3 and 0.068 g of S according to the molar ratio of 2:1:4:1 under argon atmosphere. Then, weigh 6 g of the flux CsCl with the ratio of raw material:flux = 1:2, mix it evenly with the raw materials, place them in a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then carry out melting and sealing;

[0208] b. Put the quartz tube in step a into a Bridgman furnace with programmable temperature control, heat it to 910 °C at a heating rate of 24 °C / h, and keep it at this temperature for 38 h;

[0209] c. Lower the quartz tube in step b vertically at a speed of 0.18 mm / h, and the crystal grows during the descent of the Bridgman furnace. The growth period is 15 days. After the growth is completed, keep the crystal in the Bridgman furnace for continuous annealing, and lower the temperature to room temperature at a cooling rate of 35 °C / h to obtain a cesium gallium sulfide chloride infrared nonlinear optical crystal with dimensions of 1.96×1.48×0.14 mm 3 .

[0210] Example 36

[0211] The cesium gallium chloro-sulfide infrared nonlinear optical crystal is grown by the Bridgman method. The specific operation is carried out according to the following steps:

[0212] a. Weigh 0.566 g of Cs, 0.359 g of CsCl, 2.007 g of Ga 2 S 3 and 0.068 g of S according to the molar ratio of 2:1:4:1 under argon atmosphere. Then, weigh 6 g of the flux CsCl with the raw materials:flux = 1:2, mix them evenly, place them in a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then conduct melting and sealing;

[0213] b. Put the quartz tube in step a into a Bridgman furnace with programmable temperature control, heat it to 910 °C at a heating rate of 24 °C / h, and keep it at this temperature for 38 h;

[0214] c. Place the quartz tube in step c in the Bridgman furnace, and cool the furnace temperature from 910 °C to room temperature at a cooling rate of 1.5 °C / h to obtain a cesium gallium chloro-sulfide infrared nonlinear optical crystal with dimensions of 1.98×1.46×0.16 mm 3 .

[0215] Example 37

[0216] The cesium gallium chloro-sulfide infrared nonlinear optical crystal is grown by the Bridgman method. The specific operation is carried out according to the following steps:

[0217] a. Weigh 0.849 g of Cs, 0.125 g of GaCl 3 , 1.138 g of Ga and 0.888 g of S according to the molar ratio of 9:1:23:39 under argon atmosphere. Then, weigh 9 g of the flux CsCl with the raw materials:flux = 1:3, mix them evenly, place them in a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then conduct melting and sealing;

[0218] b. Put the quartz tube in step a into a Bridgman furnace with programmable temperature control, heat it to 920 °C at a heating rate of 20 °C / h, and keep it at this temperature for 36 h;

[0219] c. Vertically lower the quartz tube in step b at a speed of 0.16 mm / h, and the crystal grows during the descent of the Bridgman furnace. The growth cycle is 20 days. After the growth is completed, the crystal needs to be continuously annealed in the Bridgman furnace and cooled to room temperature at a cooling rate of 30 °C / h to obtain a cesium gallium chloro-sulfide infrared nonlinear optical crystal with dimensions of 1.98×1.46×0.16 mm 3Cesium chloro-thio-gallium infrared nonlinear optical crystal.

[0220] Example 38

[0221] The cesium chloro-thio-gallium infrared nonlinear optical crystal was grown by the Bridgman method. The specific operation was carried out according to the following steps:

[0222] a. Weigh 0.849 g of Cs, 0.125 g of GaCl 3 , 1.138 g of Ga and 0.888 g of S according to the molar ratio of 9:1:23:39 under argon atmosphere. Then, weigh 9 g of the flux CsCl with the raw materials:flux = 1:3, mix them evenly, place them in a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then perform melting and sealing.

[0223] b. Place the quartz tube in step a into a Bridgman furnace with programmable temperature control, heat it to 920 °C at a heating rate of 20 °C / h, and keep it at this temperature for 36 h.

[0224] c. Place the quartz tube in step b in the Bridgman furnace, and cool the furnace temperature from 920 °C to room temperature at a cooling rate of 1.0 °C / h to obtain a cesium chloro-thio-gallium infrared nonlinear optical crystal with dimensions of 1.94×1.44×0.20 mm 3 .

[0225] Example 39

[0226] The cesium chloro-thio-gallium infrared nonlinear optical crystal was grown by the Bridgman method. The specific operation was carried out according to the following steps:

[0227] a. Weigh 0.849 g of Cs, 0.125 g of GaCl 3 , 1.924 g of Ga 2 S 3 and 0.102 g of S according to the molar ratio of 18:2:23:9 under argon atmosphere. Then, weigh 12 g of the flux CsCl with the raw materials:flux = 1:4, mix them evenly, place them in a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then perform melting and sealing.

[0228] b. Place the quartz tube in step a into a Bridgman furnace with programmable temperature control, heat it to 930 °C at a heating rate of 22 °C / h, and keep it at this temperature for 34 h.

[0229] c. Lower the quartz tube in step b vertically at a speed of 0.14 mm / h. The crystal grows during the descent of the crucible in the descending furnace. The growth period is 25 days. After the growth is completed, anneal the crystal continuously in the crucible descending furnace and cool it to room temperature at a rate of 25 °C / h to obtain a CsGaS₂Cl infrared nonlinear optical crystal with dimensions of 2.00×1.44×0.18 mm. 3 of CsGaS₂Cl infrared nonlinear optical crystal.

[0230] Example 40

[0231] To grow a CsGaS₂Cl infrared nonlinear optical crystal by the Bridgman method, the specific operations are carried out according to the following steps:

[0232] a. Weigh 0.849 g of Cs, 0.125 g of GaCl 3 , 1.924 g of Ga 2 S 3 and 0.102 g of S according to the molar ratio of 18:2:23:9 under argon atmosphere. Then, weigh 12 g of the flux CsCl with a raw material to flux ratio of 1:4, mix it evenly with the raw materials, place them in a quartz tube with a length of 24 cm and a diameter of 12 mm, and evacuate the air pressure in the quartz tube to 10 -3 Pa and then perform melting and sealing.

[0233] b. Put the quartz tube in step a into a programmable temperature-controlled crucible descending furnace, heat it to 930 °C at a heating rate of 22 °C / h, and keep it at this temperature for 34 h.

[0234] c. Place the quartz tube in step b in the crucible descending furnace, and lower the furnace temperature from 930 °C to room temperature at a rate of 1.5 °C / h to obtain a CsGaS₂Cl infrared nonlinear optical crystal with dimensions of 2.00×1.46×0.16 mm. 3 of CsGaS₂Cl infrared nonlinear optical crystal.

[0235] Example 41

[0236] To grow a CsGaS₂Cl infrared nonlinear optical crystal by the Bridgman method, the specific operations are carried out according to the following steps:

[0237] a. Weigh 0.952 g of Cs 2 S, 0.125 g of GaCl 3 , 1.138 g of Ga and 0.785 g of S according to the molar ratio of 9:2:46:69 under argon atmosphere. Then, weigh 15 g of the flux CsCl with a raw material to flux ratio of 1:5, mix it evenly with the raw materials, place them in a quartz tube with a length of 24 cm and a diameter of 12 mm, and evacuate the air pressure in the quartz tube to 10 -3 Pa and then perform melting and sealing.

[0238] b. Place the quartz tube in step a into a crucible lowering furnace with programmable temperature control, heat it to 940 °C at a heating rate of 26 °C / h, and hold the temperature for 32 h;

[0239] c. Lower the quartz tube in step b vertically at a speed of 0.12 mm / h. The crystal grows during the lowering process of the crucible in the furnace. The growth period is 30 days. After the growth is completed, the crystal needs to be continuously annealed in the crucible lowering furnace and cooled to room temperature at a cooling rate of 20 °C / h to obtain a cesium chloro-thio-gallate infrared nonlinear optical crystal with dimensions of 2.02×1.46×0.12 mm. 3

[0240] Example 42

[0241] To grow a cesium chloro-thio-gallate infrared nonlinear optical crystal by the Bridgman method, the specific operation is carried out according to the following steps:

[0242] a. Weigh 0.952 g of Cs 2 S, 0.125 g of GaCl 3 , 1.138 g of Ga and 0.785 g of S according to the molar ratio of 9:2:46:69 under argon atmosphere. Then, weigh 15 g of the flux CsCl with a raw material:flux ratio of 1:5, and mix it evenly with the raw materials;

[0243] b. Place the raw materials and flux weighed in step a into a quartz tube with a length of 24 cm and a diameter of 12 mm under argon atmosphere, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then carry out melting and sealing;

[0244] c. Place the quartz tube in step b into a crucible lowering furnace, and lower the furnace temperature from 940 °C to room temperature at a cooling rate of 2.0 °C / h to obtain a cesium chloro-thio-gallate infrared nonlinear optical crystal with dimensions of 2.04×1.50×0.16 mm. 3

[0245] Example 43

[0246] To grow a cesium chloro-thio-gallate infrared nonlinear optical crystal by the Bridgman method, the specific operation is carried out according to the following steps:

[0247] a. Weigh 0.951 g of Cs 2 S, 0.125 g of GaCl 3 and 1.924 g of Ga 2 S 3 , and then weigh 12 g of the flux CsCl with a raw material:flux ratio of 1:4, mix it evenly with the raw materials, place it into a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3After that, perform melting and sealing under 10 Pa;

[0248] b. Place the quartz tube in step a into a crucible lowering furnace with programmable temperature control, heat it to 950 °C at a heating rate of 30 °C / h, and keep it at this temperature for 30 h;

[0249] c. Vertically lower the quartz tube in step b at a speed of 0.10 mm / h. The crystal grows during the lowering process of the crucible in the crucible lowering furnace. The growth period is 35 days. After the growth is completed, continuously anneal the crystal in the crucible lowering furnace and cool it to room temperature at a cooling rate of 15 °C / h to obtain a CsGaS₂Cl infrared nonlinear optical crystal with dimensions of 2.04×1.48×0.14 mm 3

[0250] Example 44

[0251] To grow a CsGaS₂Cl infrared nonlinear optical crystal by the crucible lowering method, the specific operations are carried out according to the following steps:

[0252] a. Weigh 0.951 g of Cs 2 S, 0.125 g of GaCl 3 and 1.924 g of Ga 2 S 3 under argon conditions according to a molar ratio of 9:2:23. Then, weigh 12 g of the flux CsCl with a raw material:flux ratio of 1:4, mix it evenly with the raw materials, place them in a quartz tube with a length of 24 cm and a diameter of 12 mm, and use a vacuum pump to pump the air pressure in the quartz tube to 10 -3 Pa and then perform melting and sealing;

[0253] b. Place the quartz tube in step a into a crucible lowering furnace with programmable temperature control, heat it to 950 °C at a heating rate of 30 °C / h, and keep it at this temperature for 30 h;

[0254] c. Place the quartz tube in step b in the crucible lowering furnace, and lower the furnace temperature from 950 °C to room temperature at a cooling rate of 1.0 °C / h to obtain a CsGaS₂Cl infrared nonlinear optical crystal with dimensions of 2.06×1.44×0.18 mm 3

[0255] Example 45

[0256] Place any one of the CsGaS₂Cl infrared nonlinear optical crystals obtained in Examples 9 - 44 at the position shown in Figure 4 3. At room temperature, use the 2090 nm output of a Q-switched Ho:Tm:Cr:YAG laser as the light source, and 1045 nm frequency-doubled light output can be observed. The output intensity is 0.6 times that of AGS under the same conditions ( Figure 3 ).

[0257] Example 46

[0258] Any one of the Cs obtained in Examples 9-44 3 Ga 8 S 13 Cl infrared nonlinear optical crystal is placed at the position of 3 as shown, where 1 is a laser, 2 is a convex lens, Hg Figure 4 shown, and 1 is a laser, 2 is a convex lens, Hg 7 P 2 Se 12 infrared nonlinear optical crystal, 4 is a prism, 5 is a filter; the laser beam emitted by the laser 1 passes through the convex lens 2 and enters the Cs 3 Ga 8 S 13 Cl crystal 3, and the generated output laser beam passes through the prism 4 and the filter 5, so as to obtain the required laser beam.

[0259] Using the Cs 3 Ga 8 S 13 devices made of Cl infrared nonlinear optical crystals can be frequency doubling generators, up and down frequency converters, optical parametric oscillators, and optical parametric amplifiers.

[0260] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not restrictive. Although the present invention has been described in detail with reference to the embodiments, those of ordinary skill in the art should understand that any modification or equivalent replacement of the technical solutions of the present invention does not depart from the spirit and scope of the technical solutions of the present invention.

Claims

1. A compound cesium gallium chlorosulfide, characterized in that, The molecular formula of this compound is Cs 3 Ga 8 S 13 Cl, with a molecular weight of 1408.

72. Its structure belongs to the monoclinic system, and the space group is Cc , and it is prepared by the flux method.

2. The preparation method of the compound cesium gallium chlorosulfide according to claim 1, characterized in that it is carried out according to the following steps: a. According to the chemical formula Cs 3 Ga 8 S 13 Cl, weigh the raw materials in a molar ratio of Cs∶Ga∶S∶Cl = 3∶8∶13∶1 under argon conditions, and mix them evenly with the flux; then load the mixture into a quartz container and evacuate it to 10 -3 Pa for melting and sealing; the Cs raw material is Cs, Cs 2 S or CsCl; the Ga raw material is Ga, Ga 2 S 3 or GaCl 3 , and the sulfur raw material is S; the flux is CsCl, and the ratio of raw material∶flux = 1∶1 - 5; b. Place the sealed sample in step a in a muffle furnace, heat it to 850 - 900 °C at a rate of 10 - 40 °C / h, keep it at a constant temperature for 20 - 30 h; then cool it to room temperature at a rate of 10 - 20 °C / h, take it out, put it into a mortar and pestle it, wash the flux with deionized water to obtain a powdered pure sample of cesium gallium chlorosulfide.

3. A cesium gallium chlorosulfide infrared nonlinear optical crystal, characterized in that, The chemical formula of the crystal is Cs 3 Ga 8 S 13 Cl, with a molecular weight of 1408.72, crystallizes in the monoclinic system, and the space group is Cc , and the unit cell parameters are a = 10.0698(5) Å, b = 17.8139(8) Å, c = 14.6479(6) Å; α = 90°, β = 90.218(2)°, γ = 90°, V = 2627.56(20) Å 3 .

4. The preparation method of the cesium gallium chlorosulfide infrared nonlinear optical crystal according to claim 3, characterized in that, it is prepared by the flux method and the Bridgman method: For the growth of the cesium gallium chlorosulfide infrared nonlinear optical crystal by the flux method, the specific operation is carried out according to the following steps: a. According to the chemical formula Cs 3 Ga 8 S 13 Cl, the molar ratio of Cs∶Ga∶S∶Cl = 3∶8∶13∶1, is mixed evenly with a flux; it is loaded into a quartz tube, and the quartz tube is evacuated to a vacuum degree of 10 -3 Pa by a vacuum pump and then melted and sealed. Among them, the Cs source material is Cs, Cs 2 S or CsCl; the Ga source material is Ga, Ga 2 S 3 or GaCl 3 ; the flux is CsCl, and the raw material∶flux = 1∶1 - 5; b. Place the quartz tube in step a in a programmable temperature-controlled muffle furnace, heat it to 850 - 900 °C at a heating rate of 10 - 20 °C / h, keep it at a constant temperature for 20 - 30 h, and then cool it to room temperature at a cooling rate of 4 - 6 °C / h to obtain a cesium gallium chlorosulfide infrared nonlinear optical crystal; For the growth of the cesium gallium chlorosulfide infrared nonlinear optical crystal by the Bridgman method, the specific operation is carried out according to the following steps: a. According to the chemical formula Cs 3 Ga 8 S 13 Cl, the molar ratio of Cs∶Ga∶S∶Cl = 3∶8∶13∶1, is mixed evenly with a cosolvent; filled into a quartz tube, and the quartz tube is evacuated to 10 -3 Pa for melting and sealing, where the Cs source material is Cs, Cs 2 S or CsCl; The Ga source materials are Ga, Ga 2 S 3 or GaCl 3 ; the flux is CsCl, and the ratio of raw material to flux is 1:1 - 5; b. Place the quartz tube in step a in a programmable temperature-controlled Bridgman furnace, heat it to 900 - 950 °C at a heating rate of 20 - 30 °C / h, and keep it at a constant temperature for 30 - 40 h; c. Lower the quartz tube in step b vertically at a speed of 0.1 - 0.2 mm / h, and the crystal grows during the descent of the Bridgman furnace. The growth period is 10 - 40 days. After the growth is completed, the crystal needs to be continuously annealed in the Bridgman furnace, and cooled to room temperature at a cooling rate of 20 - 40 °C / h to obtain a cesium gallium chlorosulfide infrared nonlinear optical crystal; Or place the quartz tube in step b in a Bridgman furnace, and cool the furnace temperature from 900 - 950 °C to room temperature at a cooling rate of 1 - 2 °C / h to obtain a cesium gallium chlorosulfide infrared nonlinear optical crystal.

5. The use of the cesium gallium chlorosulfide infrared nonlinear optical crystal according to claim 3 in the preparation of infrared all-solid-state lasers, infrared laser-guided radars, laser medical treatments, or medium- and long-distance laser communications.

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