A salt-containing chalcogenide crystal material, a preparation method thereof and application thereof as an infrared nonlinear optical material

Abstract

The application discloses a salt-containing chalcogenide crystal material, a preparation method thereof and application thereof as an infrared nonlinear optical material, and belongs to the technical field of crystal preparation. The salt-containing chalcogenide has a diamond-like structure; the chemical formula of the salt-containing chalcogenide is one of [A5X][M 14 Q 23 ], [A5BaX][M 18 Q 30 ], [A 13 BaX5][M 22 Q 38 ], [A 14 LiX5][M 22 Q 38 ]; wherein A is at least one selected from Na, K, Rb and Cs; X is at least one selected from Cl, Br and I; M is at least one selected from Ga and In; and Q is at least one selected from S, Se and Te. The NLO effect of the material is 0.3-10 times that of a commercial AgGaS2, the laser damage threshold is 1-50 times that of AgGaS2, and the comprehensive performance is greatly improved, so that the material is a potential infrared NLO material.

Description

Technical Field

[0001] This application relates to a salt-containing sulfide compound crystal material, its preparation method, and its application as an infrared nonlinear optical material, belonging to the field of crystal preparation technology. Background Technology

[0002] Nonlinear optical (NLO) crystals, exhibiting frequency conversion effects on lasers, have attracted worldwide attention as crucial optical materials in the laser field. In the visible-near-infrared and ultraviolet bands, high-performance crystal materials such as β-BaB₂O₄, LiB₃O₅, KH₂PO₄, and KTiPO₄ fully meet application requirements. Currently, AgGaQ₂ (Q = S, Se) and ZnGeP₂, possessing strong second harmonic generation (SHG) signals and wide infrared transparency, are commercially available mid-to-far-infrared NLO crystals. However, their application in high-power lasers is limited by inherent drawbacks such as low laser-induced damage threshold (LIDT) and two-photon absorption. Therefore, new potential infrared NLO materials remain to be investigated. These should possess strong SHG signals and large optical band gaps to achieve high laser damage thresholds; however, in chalcogenides, strong NLO effects often result in low laser damage thresholds. Therefore, the current focus and challenge in the research of NLO crystals in the mid- and far-infrared bands is the lack of NLO crystals that possess both a large NLO coefficient and a high laser damage threshold, in order to achieve high-power mid- and far-infrared laser output. Summary of the Invention

[0003] To address the challenge of balancing a large NLO effect and a high laser damage threshold in existing nonlinear optical (NLO) crystal technologies, this application provides a salt-containing chalcogenide compound crystal material. Its NLO effect is 0.3-10 times that of commercial AgGaS2, and its laser damage threshold is 1-50 times that of commercial AgGaS2, resulting in a significant improvement in overall performance. This material is a potential infrared NLO material.

[0004] This application adopts the following scheme:

[0005] According to one aspect of this application, a salt-containing sulfide compound crystal material is provided. The salt-containing sulfide compound crystal material has a diamond-like structure, that is, the tetrahedral structural units are connected by anionic co-points to form three-dimensional honeycomb-like hexagonal open anionic groups, and then alkali (alkaline earth) metal halides are used as salt-containing polycations to fill the anionic channels to form a three-dimensional framework structure.

[0006] The chemical formula of the salt-containing chalcogenide crystalline material is [A5X][M]. 14 Q 23 ]、[A5BaX][M 18 Q30 ],[A 13 BaX5][M 22 Q 38 ]、[A 14 LiX5][M 22 Q 38 ]one of the;

[0007] Wherein, A is selected from at least one of Na, K, Rb, and Cs;

[0008] X is selected from at least one of Cl, Br, and I;

[0009] M is selected from at least one of Ga and In;

[0010] Q is selected from at least one of S, Se, and Te.

[0011] The chemical formula is [A5X][M] 14 Q 23 [A crystalline material containing sulfide compounds, belonging to the monoclinic crystal system, space group P1;]

[0012] Preferably, the chemical formula is [A5BaX][M] 18 Q 30 [A crystalline material containing salt-containing sulfur compounds, belonging to the hexagonal crystal system, space group P63cm;]

[0013] Preferably, the chemical formula is [A 13 BaX5][M 22 Q 38 [A crystalline material containing sulfide compounds, belonging to the monoclinic crystal system, space group C2;]

[0014] Preferably, the chemical formula is [A 14 LiX5][M 22 Q 38 [ ] is a salt-containing sulfur-containing crystalline material belonging to the monoclinic crystal system, space group C2.

[0015] Optionally, the chemical formula is [A5X][M] 14 Q 23 The cell parameters of the salt-containing chalcogenide crystalline material are a = 8.5671(2) - 10.2638(2); α=92.193(2)-94.162(1)°, β=93.436(2)-95.483(1)°, γ=97.838(2)-99.748(2)°, Z = 1.

[0016] Optionally, the chemical formula is [A5BaX][M] 18 Q 30The unit cell parameters of the salt-containing chalcogenide crystalline material are as follows: α=β=90°, γ=120°, Z = 2.

[0017] Optionally, the chemical formula is [A 13 BaX5][M 22 Q 38 The unit cell parameters of the salt-containing chalcogenide crystalline material are as follows: α=γ=90°, γ=124.124(9)-126.158(1)°, Z = 2.

[0018] Optionally, the chemical formula is [A 14 LiX5][M 22 Q 38 The unit cell parameters of the salt-containing chalcogenide crystalline material are as follows: α=γ=90°, γ=124.785(9)-126.258(9)°, Z = 2.

[0019] Optionally, the laser damage threshold of the salt-containing sulfide compound crystal material powder is 1 to 50 times that of AgGaS2.

[0020] Optionally, the laser damage threshold of the salt-containing sulfide compound crystal material powder is 15 to 45 times that of AgGaS2.

[0021] Optionally, the overtone intensity of the salt-containing chalcogenide crystal material is 0.3-10 times that of AgGaS2.

[0022] Optionally, the overtone intensity of the salt-containing sulfide compound crystal material is 0.3-2.1 times that of AgGaS2.

[0023] According to another aspect of this application, a method for preparing the above-mentioned salt-containing chalcogenide crystalline material is provided, comprising the following steps:

[0024] The raw material mixture is placed into a reaction vessel, sealed under vacuum, heated to the reaction temperature, and reacted to obtain the salt-containing sulfide compound crystal material.

[0025] The raw material mixture is placed into a reaction vessel, sealed under vacuum, heated to the reaction temperature, and reacted to obtain the salt-containing sulfide compound crystal material.

[0026] The raw material mixture is obtained by mixing raw materials containing elements M, Q, AX, and LiX in a molar ratio of Ba:M:Q:AX:LiX = 1:(5-6):(6-12):(3-5):(0.5-1.5) until homogeneous. The chemical formula of the salt-containing chalcogenide crystalline material is [A5X][In]. 14 Q 23 ];

[0027] The raw material mixture is obtained by mixing raw materials containing Ba, M, Q, AX, and LiX in a molar ratio of Ba:M:Q:AX:LiX = 1:(6.5-7):(6-12):(3-5):(0.5-1.5) until homogeneous. The chemical formula of the salt-containing chalcogenide crystalline material is [A5BaX][In]. 18 Q 30 ];

[0028] The raw material mixture is obtained by mixing raw materials containing Ba, M, Q, AX, and LiX in a molar ratio of Ba:M:Q:AX:LiX = 1:(3-4.5):(6-9):(7-12):(0.5-1.5) until homogeneous. The chemical formula of the salt-containing chalcogenide crystalline material is [A]. 13 BaX5][In 22 Q 38 ];

[0029] The raw material mixture is obtained by mixing raw materials containing elemental Li, element M, element Q, element Ax, and element LiX in a molar ratio of Ba:M:Q:AX:Li:LiX = 1:(3-4.5):(6-9):(7-12):(1-2):(0.5-1.5) until homogeneous. The chemical formula of the salt-containing chalcogenide crystalline material is [A...]. 14 LiX5][In 22 Q 38 ].

[0030] The method for preparing salt-containing chalcogenide crystalline materials in this application involves both reaction products and byproducts, including BaX2, BaM2Q3, and AMQ2. Ba initially binds to the AX fluxing agent in the reaction, abstracting X: Ba + 2AX → BaX2 + 2A. Additionally, LiX acts as a fluxing agent with AX, facilitating the reaction. Samples are then manually selected from the reaction products for testing various physical properties.

[0031] In this application, different diamond-like structures can be formed by varying the ratio of raw materials used.

[0032] Optionally, in the raw material mixture, the source of element M is selected from at least one of elemental M and M2Q3;

[0033] The source of element Q is selected from at least one of elemental Q, BaQ, and In2Q3;

[0034] The source of Ba element is selected from at least one of Ba elemental and BaQ;

[0035] The source of element A is selected from at least one of element A and AX.

[0036] Optionally, the reaction conditions are as follows:

[0037] The reaction temperature is 600℃~1100℃, and the reaction time is 1h~200h.

[0038] Optionally, the reaction temperature is reached by heating, wherein the heating rate is 1°C / h to 60°C / h.

[0039] Optionally, cooling is required after the reaction;

[0040] The cooling is either natural cooling or cooling at a rate of 1℃ / h-10℃ / h to 200-40℃ followed by natural cooling.

[0041] Optionally, the pressure range inside the reaction vessel after vacuuming is 10. -3 Pa-10Pa.

[0042] Optionally, the sealing method is welding sealing.

[0043] Optionally, the reaction vessel is a quartz tube.

[0044] According to another aspect of this application, the above-mentioned salt-containing sulfide compound crystal material or the salt-containing sulfide compound crystal material obtained according to the above preparation method is also provided as a nonlinear optical crystal for use in the field of lasers.

[0045] The beneficial effects that this application can produce include:

[0046] The salt-containing sulfide compound crystal material provided in this application has a frequency doubling effect that is 0.3-20 times that of commercial AgGaS2, and a laser damage threshold that is 1-50 times that of commercial AgGaS2, showing a significant improvement in performance and making it a potential infrared nonlinear optical material. Attached Figure Description

[0047] Figure 1 [K5Cl][In] prepared for the embodiments of this application 14 Se 23 Powder diffraction pattern of ];

[0048] Figure 2 [Rb5Cl][In] prepared for the embodiments of this application 14 Se 23 Powder diffraction pattern of ];

[0049] Figure 3 [K5BaCl][In] prepared for the embodiments of this application 18 Se 30 Powder diffraction pattern of ];

[0050] Figure 4 [Rb5BaCl][In] prepared for the embodiments of this application 18 Se 30 Powder diffraction pattern of ];

[0051] Figure 5 [K] prepared for the embodiments of this application 13 BaCl5][In 22 Se 38 Powder diffraction pattern;

[0052] Figure 6 [K] prepared for the embodiments of this application 14 LiCl5][In 22 Se 38 Powder diffraction pattern;

[0053] Figure 7 [K5Cl][In] prepared in the embodiments of this application at 1910 nm 14 Se 23 ]、[Rb5Cl][In 14 Se 23 ]、[K5BaCl][In 18 Se 30 ] 、 [Rb5BaCl][In 18 Se 30 ] 、 [K 13 BaCl5][In 22 Se 38 ]、[K 14 LiCl5][In 22 Se 38 Frequency harmonics of polycrystalline powder;

[0054] Figure 8 [K5Cl][In] prepared for the embodiments of this application 14 Se 23 The crystal structure of ];

[0055] Figure 9 [K5BaCl][In] prepared for the embodiments of this application18 Se 30 The crystal structure of ];

[0056] Figure 10 [K] prepared for the embodiments of this application 13 BaCl5][In 22 Se 38 The crystal structure of ];

[0057] Figure 11 [K] prepared for the embodiments of this application 14 LiCl5][In 22 Se 38 The crystal structure of ]. Detailed Implementation

[0058] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0059] Unless otherwise specified, the raw materials used in the embodiments of this application were purchased commercially.

[0060] The instrument used for single-crystal X-ray diffraction was a Rigaku FR-X micro-focusing diffractometer.

[0061] Test conditions: 293K, structural analysis was performed using SHELXTL crystallography software.

[0062] The instrument used for powder X-ray diffraction was a Rigaku Flex600 X-ray diffractometer.

[0063] Test conditions: 293K.

[0064] The method for calculating the laser damage threshold described in this application uses a VIBRANTHE 355LD laser instrument manufactured by OPOTEK Corporation, USA. First, Example 1 and commercially available AgGaS2 (Comparative Example 1) were sieved to select particles with a diameter range of 150-200 nm. These particles were then placed under a 1064 nm laser beam with a pulse width of 10 ns. The surface damage of the samples was observed by continuously increasing the laser power. When a damaged spot appeared on the sample, the laser power was recorded, and the size of the damaged spot was measured. The laser power / damage area was used as the laser damage threshold value for comparison.

[0065] The frequency doubling signal testing method described in this application involves screening the sample crystal and the AgGaS2 crystal used as a reference using standard sieves to select crystals with particle sizes in five ranges: 30-50, 50-75, 75-100, 100-150, and 150-200 nm. These samples are then mounted separately and placed under a laser optical path. Their nonlinear optical properties are tested using a near-infrared charge-coupled detector at a laser intensity of 1910 nm. A graph is then plotted with particle size as the abscissa and the measured nonlinear optical properties as the ordinate to determine the magnitude of the nonlinear optical properties of the crystal material and the phase matching of the crystal material.

[0066] Example 1

[0067] Ba (31 mg), In (130 mg), S (51 mg), NaBr (70 mg), and LiBr (20 mg) were mixed thoroughly and then placed into a quartz tube and evacuated to 10°C. -2 The tube was sealed with Pa and slowly heated to 710°C in a muffle furnace. After holding at this temperature for 15 hours, the temperature was lowered to 400°C at a rate of 3°C / h. The furnace was then turned off and allowed to cool naturally to room temperature, yielding the product with the chemical formula [Na₅Br][In]. 14 S 23 ] crystals.

[0068] Example 2

[0069] Ba (39 mg), Ga (100 mg), Te (258 mg), CsI (157 mg), and LiI (22 mg) were mixed thoroughly and then placed into a quartz tube and evacuated to 10°C. -3 The Pa tube was sealed and slowly heated to 620°C in a muffle furnace. After holding at that temperature for 72 hours, the temperature was lowered to 400°C at a rate of 4°C / h. The furnace was then turned off and allowed to cool naturally to room temperature, yielding the product with the chemical formula [Cs5I][Ga]. 14 Te 23 ] crystals.

[0070] Example 3

[0071] Ba (38 mg), In (159 mg), Se (200 mg), RbCl (150 mg), and LiCl (18 mg) were mixed thoroughly and placed in a quartz tube. The tube was then evacuated to 1 Pa and sealed. The mixture was placed in a muffle furnace and slowly heated to 850°C. After holding at this temperature for several hundred hours, the temperature was lowered to 400°C at a rate of 3°C / h. The furnace was then turned off and allowed to cool naturally to room temperature, yielding the chemical formula [Rb5Cl][In]. 14 Se 23 The crystal, its powder diffraction pattern is as follows: Figure 2 As shown.

[0072] Example 4

[0073] Ba (33 mg), In (142 mg), Se (175 mg), KCl (104 mg), and LiCl (16 mg) were mixed thoroughly and placed in a quartz tube. The tube was then evacuated to 10 Pa and sealed. The mixture was placed in a muffle furnace and slowly heated to 870°C. After holding at this temperature for several hundred hours, the temperature was lowered to 300°C at a rate of 5°C / h. The furnace was then turned off and allowed to cool naturally to room temperature, yielding the chemical formula [K₅Cl][In]. 14 Se 23 The crystal is shown below. Its powder diffraction pattern is as follows: Figure 1 As shown, the crystal structure diagram is as follows: Figure 8 As shown.

[0074] Example 5

[0075] Ba (53 mg), Ga (250 mg), Te (61 mg), NaI (150 mg), and LiI (25 mg) were mixed thoroughly and then placed into a quartz tube and evacuated to 10°C. -3 The Pa tube was sealed and slowly heated to 650°C in a muffle furnace. After holding at this temperature for 120 hours, the muffle furnace was turned off and the tube was allowed to cool naturally to room temperature, yielding the chemical formula [Na5BaI][Ga]. 18 S 30 ] crystals.

[0076] Example 6

[0077] Ba (32 mg), In₂S₃ (220 mg), S (12 mg), RbBr (231 mg), and LiBr (20 mg) were mixed thoroughly and then placed into a quartz tube and evacuated to 10°C. -1 The tube was sealed with Pa and slowly heated to 950°C in a muffle furnace. After holding at that temperature for 72 hours, the muffle furnace was turned off and the tube was allowed to cool naturally to room temperature, yielding the chemical formula [Rb5BaBr][In]. 18 S 30 ] crystals.

[0078] Example 7

[0079] Ba (35 mg), In (172 mg), Se (217 mg), KCl (74 mg), and LiCl (13 mg) were mixed thoroughly and then placed into a quartz tube and evacuated to 10°C. -2 The tube was sealed with Pa and slowly heated to 850°C in a muffle furnace. After holding at this temperature for 120 hours, it was cooled to 400°C at a rate of 5°C / h. The muffle furnace was then turned off, and the tube was allowed to cool naturally to room temperature, yielding the chemical formula [K5BaCl][In]. 18 Se 30 The crystal, its powder diffraction pattern is as follows: Figure 3 As shown, the crystal structure diagram is as follows: Figure 9As shown.

[0080] Example 8

[0081] Ba (29 mg), In (144 mg), Se (199 mg), RbCl (128 mg), and LiCl (17 mg) were mixed thoroughly and then placed into a quartz tube and evacuated to 10°C. -2 The tube was sealed with Pa and slowly heated to 820°C in a muffle furnace. After holding at this temperature for 50 hours, the furnace was turned off and the tube was allowed to cool naturally to room temperature, yielding the chemical formula [Rb5BaCl][In]. 18 Se 30 The crystal, its powder diffraction pattern is as follows: Figure 4 As shown.

[0082] Example 9

[0083] Ba (52 mg), Ga (177 mg), Te (111 mg), NaBr (158 mg), and LiBr (20 mg) were mixed thoroughly and then placed into a quartz tube and evacuated to 10°C. -2 The Pa-sealed tube was placed in a muffle furnace and slowly heated to 600°C. After holding at this temperature for several hours, the muffle furnace was turned off and the tube was allowed to cool naturally to room temperature, yielding the chemical formula [Na]. 13 BaBr5][Ga 22 S 38 ] crystals.

[0084] Example 10

[0085] BaSe (48 mg), In₂Se₃ (208 mg), Se (17 mg), CsCl (225 mg), and LiCl (14 mg) were mixed thoroughly and then placed into a quartz tube and evacuated to 10°C. -2 Pa was sealed in a tube and slowly heated to 700°C in a muffle furnace. After holding at that temperature for several hundred hours, the muffle furnace was turned off and the tube was allowed to cool naturally to room temperature, yielding the chemical formula [Cs]. 13 BaCl5][In 22 Se 38 ] crystals.

[0086] Example 11

[0087] Ba (42 mg), In (143 mg), Se (222 mg), KCl (92 mg), and LiCl (16 mg) were mixed thoroughly and then placed into a quartz tube and evacuated to 10°C. -2 Pa was sealed in a tube and slowly heated to 800°C in a muffle furnace. After holding at this temperature for several hours, the muffle furnace was turned off and the tube was allowed to cool naturally to room temperature, yielding a product with the chemical formula [K]. 13 BaCl5][In 22 Se38 The crystal, its powder diffraction pattern is as follows: Figure 5 As shown, the crystal structure diagram is as follows: Figure 10 As shown.

[0088] Example 12

[0089] Ba (35 mg), In (120 mg), Se (182 mg), RbBr (158 mg), and LiCl (22 mg) were mixed thoroughly and then placed into a quartz tube and evacuated to 10°C. -2 The Pa-sealed tube was placed in a muffle furnace and slowly heated to 850°C. After holding at this temperature for 120 hours, it was cooled to 300°C at a rate of 3°C / h. The muffle furnace was then turned off, and the tube was allowed to cool naturally to room temperature, yielding the chemical formula [Rb]. 13 BaBr5][In 22 Se 38 ] crystals.

[0090] Example 13

[0091] Li (5 mg), In₂S₃ (154 mg), S (65 mg), RbI (276 mg), and LiI (27 mg) were mixed thoroughly and then placed into a quartz tube and evacuated to 10°C. -1 Pa was sealed in a tube and slowly heated to 850°C in a muffle furnace. After holding at that temperature for 72 hours, the temperature was lowered to 300°C at a rate of 3°C / h. The muffle furnace was then turned off and allowed to cool naturally to room temperature, yielding the chemical formula [Rb]. 14 LiI5][In 18 S 30 ] crystals.

[0092] Example 14

[0093] Li (2 mg), LiCl (100 mg), In (103 mg), Se (94 mg), KCl (151 mg), and LiCl (15 mg) were mixed thoroughly and then placed into a quartz tube and evacuated to 10°C. -2 Pa was sealed in a tube and slowly heated to 750°C in a muffle furnace. After holding at this temperature for 36 hours, the muffle furnace was turned off and the tube was allowed to cool naturally to room temperature, yielding the chemical formula [K]. 14 LiCl5][In 18 Se 30 The crystal, its powder diffraction pattern is as follows: Figure 6 As shown, the crystal structure diagram is as follows: Figure 11 As shown.

[0094] Example 15

[0095] Li (4 mg), LiCl (70 mg), In (178 mg), Se (164 mg), CsBr (154 mg), and LiBr (23 mg) were mixed thoroughly and then placed into a quartz tube and evacuated to 10°C. -2 The tube was sealed with Pa and slowly heated to 700°C in a muffle furnace. After holding at this temperature for several hours, it was cooled to 300°C at a rate of 4°C / h. The muffle furnace was then turned off and allowed to cool naturally to room temperature, yielding the chemical formula [Cs]. 14 LiBr5][In 22 Se 38 ] crystals.

[0096] Example 16

[0097] Li (3 mg), Ga (92 mg), Te (138 mg), CsI (240 mg), and LiI (25 mg) were mixed thoroughly and then placed into a quartz tube and evacuated to 10°C. -2 The tube was sealed with Pa and slowly heated to 550°C in a muffle furnace. After holding at that temperature for several hundred hours, it was cooled to 200°C at a rate of 5°C / h. The muffle furnace was then turned off and allowed to cool naturally to room temperature, yielding the chemical formula [Cs]. 14 LiI5][Ga 22 Te 38 ] crystals.

[0098] Test Example 1

[0099] NLO performance testing method: The sample crystal and the AgGaS2 crystal used as a reference were screened with standard sieves to select crystals with particle sizes in five ranges: 30-50, 50-75, 75-100, 100-150, and 150-200 nm. The samples were then mounted separately and placed under a laser light path. The nonlinear optical properties were tested using a near-infrared charge-coupled detector at a laser intensity of 1700 nm. The particle size was plotted on the x-axis and the measured nonlinear optical properties were plotted on the y-axis to determine the magnitude of the NLO performance of the crystal material and the phase matching of the crystal material.

[0100] Figure 7 This indicates that [K5Cl][In] 14 Se 23 ]、[Rb5Cl][In 14 Se 23 ]、[K5BaCl][In 18 Se 30 ] 、 [Rb5BaCl][In 18 Se 30 ] 、 [K 13 BaCl5][In 22 Se 38]、[K 14 LiCl5][In 22 Se 38 The harmonic frequencies of the polycrystalline powders of the compound were 2.1, 2.1, 0.8, 0.8, 2.0, and 2.0 times that of AgGaS2, with a particle size of 150-200 μm and a frequency at 1910 nm.

[0101] Test Example 2

[0102] Laser damage threshold test of samples: The sample crystal and the AgGaS2 crystal used as a reference were screened with standard sieves to select crystals with a particle size range of 150-200nm. The samples were then placed under a 1064nm laser with a pulse width of 10ns. The laser power was continuously increased, and the damage on the sample surface was observed until a damage spot appeared on the sample. The laser power at this time was recorded, and the size of the damage spot was measured. The laser damage threshold of the sample can be calculated.

[0103] The results are shown in Table 1. At 1064 nm, [A5X][In] 14 Q 23 ],[A5BaX][In 18 Q 30 ],[A 13 BaX 10 ][In 22 Q 38 ], [A 14 LiX 10 ][In 22 Q 38 A comparison of laser damage thresholds for [Na₅Br][In](A=Na, K, Rb, Cs; X=Cl, Br, I; Q=S, Se) and AgGaS₂ polycrystalline powders, where [Na₅Br][In] 14 S 23 ],[Cs5I][Ga 14 Te 23 ],[Rb5Cl][In 14 Se 23 ],[K5Cl][In 14 Se 23 [Na5BaI][Ga] 18 Te 30 ]、[Rb5BaBr][In 18 S 30 ]、[K5BaCl][In 18 Se 30 ]、[Rb5BaCl][In 18 Se 30 ]、[Na 13 BaI5][Ga 22 Te38 ]、[Cs 13 BaCl5][In 22 S 38 ]、[K 13 BaCl5][In 22 Se 38 ]、[Rb 13 BaBr5][In 22 Se 38 ]、[Rb 14 LiI5][In 22 S 38 ]、[K 14 LiCl5][In 22 Se 38 ]、[Cs 14 LiBr5][In 22 Se 38 ]、[Cs 14 LiI5][Ga 22 Te 38 The laser damage threshold of [] is 34.5, 8.0, 16.4, 15.0, 8.5, 19.1, 14.7, 14.2, 15.0, 44.7, 15.3, 16.4, 20.1, 17.0, 16.9 and 7.0 times that of AgGaS2.

[0104] Table 1

[0105]

[0106] Test Example 3

[0107] Crystallographic data were tested on Examples 1-16, and the results can be summarized as follows:

[0108] [Na5Br][In 14 S 23 It belongs to the P1 space group of the monoclinic crystal system. α=92.3°, β=93.8°, γ=97.9°,

[0109] [Cs5I][Ga 14 Te 23 It belongs to the P1 space group of the monoclinic crystal system. α=94.16°, β=95.58°, γ=99.7°,

[0110] [Rb5Cl][In 14 Se 23 It belongs to the P1 space group of the monoclinic crystal system. α=93.6°, β=94.8°, γ=99.2°,

[0111] [K5Cl][In 14 Se 23 It belongs to the P1 space group of the monoclinic crystal system. α=93.2°, β=94.4°, γ=98.8°,

[0112] [Na5BaI][Ga 18 Te 30 It belongs to the hexagonal crystal system, space group P63cm. α=β=90°, γ=120°,

[0113] [Rb5BaBr][In 18 S 30 It belongs to the hexagonal crystal system, space group P63cm. α=β=90°, γ=120°,

[0114] [K5BaCl][In 18 Se 30 It belongs to the hexagonal crystal system, space group P63cm. α=β=90°, γ=120°,

[0115] [Rb5BaCl][In 18 Se 30 It belongs to the hexagonal crystal system, space group P63cm. α=β=90°, γ=120°,

[0116] [Na 13 BaI 10 ][Ga 22 Te 38 It belongs to the monoclinic crystal system, space group C2. α=γ=90°, β=125.6°,

[0117] [Cs 13 BaCl5][In 22 S 38It belongs to the monoclinic crystal system, space group C2. α=γ=90°, β=125.6°,

[0118] [K 13 BaCl5][In 22 Se 38 It belongs to the monoclinic crystal system, space group C2. α=γ=90°, β=125.1°,

[0119] [Rb 13 BaBr5][In 22 Se 38 It belongs to the monoclinic crystal system, space group C2. α=γ=90°, β=125.3v,

[0120] [Rb 14 LiI5][In 22 S 38 [, belongs to the monoclinic crystal system, space group C2] α=γ=90°, β=124.2°,

[0121] [K 14 LiCl5][In 22 Se 38 [, belongs to the monoclinic crystal system, space group C2] α=γ=90°, β=125.1°,

[0122] [Cs 14 LiBr5][In 22 Se 38 [, belongs to the monoclinic crystal system, space group C2] α=γ=90°, β=125.2°,

[0123] [Cs 14 LiI5][Ga 22 Te 38 [, belongs to the monoclinic crystal system, space group C2] α=γ=90°, β=125.8°,

[0124] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A crystalline material containing a salt-containing chalcogenide compound, characterized in that, The chemical formula of the salt-containing chalcogenide crystal material is [A5BaX][M 18 Q 30 ]; The chemical formula of the salt-containing chalcogenide crystalline material is specifically [Na5BaI][Ga]. 18 S 30 ]、[Rb5BaBr][In 18 S 30 ]、[K5BaCl][In 18 Se 30 ]、[Rb5BaCl][In 18 Se 30 ]; Among them, [Na5BaI][Ga 18 Te 30 ], belongs to the hexagonal crystal system P6 3 cm Space group, a = b =12.2 Å, c = 20.8 Å, α =β = 90︒, γ = 120︒, V = 4643.2 Å 3 ; [Rb5BaBr][In 18 S 30 ], belonging to the hexagonal crystal system P6 3 cm Space group, a = b =10.5 Å, c = 19.0 Å, α = β =90︒, γ = 120︒, V = 3142.2 Å 3 ; [K5BaCl][In 18 Se 30 ], belonging to the hexagonal crystal system P6 3 cm Space group, a = b =11.0 Å, c = 19.6 Å, α = β =90︒, γ = 120︒, V = 3343.3 Å 3 ; [Rb5BaCl][In 18 Se 30 ], belonging to the hexagonal crystal system P6 3 cm Space group, a = b =11.3 Å, c = 19.9 Å, α = β =90︒, γ = 120︒, V = 3811.5 Å 3 .

2. The salt-containing chalcogenide crystalline material according to claim 1, characterized in that, The laser damage threshold of the salt-containing sulfide compound crystal material powder is 1 to 50 times that of AgGaS2.

3. The salt-containing chalcogenide crystalline material according to claim 1, characterized in that, The frequency doubling intensity of the salt-containing sulfide compound crystal material is 0.3-10 times that of AgGaS2.

4. The method for preparing the salt-containing chalcogenide crystalline material according to any one of claims 1 to 3, characterized in that, Includes the following steps: The raw material mixture is placed into a reaction vessel, sealed under vacuum, heated to the reaction temperature, and reacted to obtain the salt-containing sulfide compound crystal material. The raw material mixture is obtained by mixing raw materials containing Ba, M, Q, AX, and LiX in a molar ratio of Ba:M:Q:AX:LiX = 1:(6.5~7):(6~12):(3-5):(0.5~1.5) until homogeneous. The chemical formula of the salt-containing chalcogenide crystalline material is [A5BaX][In]. 18 Q 30 ].

5. The preparation method according to claim 4, characterized in that, The conditions for the reaction are: The reaction temperature is 600°C ~ 1100°C, and the reaction time is 1 h ~ 200 h.

6. The preparation method according to claim 5, characterized in that, The reaction temperature is reached by heating at a rate of 1°C / h to 60°C / h.

7. The preparation method according to claim 4, characterized in that, Cooling is required after the reaction; The cooling is either natural cooling or cooling at a rate of 1°C / h-10°C / h to 200°C-400°C followed by natural cooling.

8. The preparation method according to claim 4, characterized in that, After vacuuming, the pressure range inside the reaction vessel is 10. -3 Pa -10Pa.

9. The application of the salt-containing sulfide compound crystal material according to any one of claims 1 to 3 or the salt-containing sulfide compound crystal material obtained by the preparation method according to any one of claims 4 to 8 as a nonlinear optical crystal in the field of lasers.

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