Sulfur-gallium-silver-sodium compound, sulfur-gallium-silver-sodium infrared nonlinear optical crystal, preparation method and application

Abstract

The invention relates to a sulfur-gallium-silver-sodium compound and a sulfur-gallium-silver-sodium infrared nonlinear optical crystal as well as a preparation method and application thereof, the molecular formula of the compound is NaAg3Ga8S14, the molecular weight is 1353.20 g / mol, the compound has an asymmetric center and is crystallized in a Cm space group of a monoclinic system, and the cell parameters are as follows: a is equal to 12.2616 (8), b is equal to 11.0956 (7), c is equal to 9.2131 (6), beta is equal to 114.981 (2) degrees, Z is equal to 2, and the volume is 1136.18 (13) 3. The crystal is prepared by a high-temperature melt method, a chemical vapor transport method or a Bridgman-Stockbarger method. The crystal has the advantages of being high in laser damage resistance, moderate in nonlinear optical effect, wide in light-transmitting wave band, large in hardness, good in mechanical performance, not prone to fragmentation and deliquescence, easy to process and store and the like, and can be used for manufacturing infrared nonlinear optical devices.

Description

Technical Field

[0001] The present invention belongs to the field of preparation of infrared nonlinear optical crystals, and particularly relates to a compound sodium silver gallium sulfide (NaAg3Ga8S 14 ), a sodium silver gallium sulfide infrared nonlinear optical crystal, and a preparation method and application thereof. Background Art

[0002] Affected by the selective absorption of atmospheric molecules, three main transmission windows are formed during the atmospheric transmission of infrared radiation, namely near-infrared (1-3 μm), mid-infrared (3-5 μm), and far-infrared (8-12 μm). Among them, the two bands of 3-5 μm and 8-12 μm have excellent atmospheric transmission characteristics, such as low molecular absorption coefficient, weak aerosol scattering effect, and high sea-level transmittance, etc., which can significantly improve the long-distance transmission ability of lasers and reduce energy loss. They are the core working bands in fields such as laser communication, infrared countermeasure, infrared ranging, remote sensing, and infrared spectroscopy, and have very important application values. At present, using nonlinear optical technologies (such as difference frequency generation (DFG), optical parametric oscillation (OPO), and optical parametric amplification (OPA)) to perform frequency conversion on existing laser light sources is the key technical approach to realizing laser output in the mid- and far-infrared bands, and infrared nonlinear optical crystals play a core material role in this process. In recent decades, the research on mid- and far-infrared nonlinear optical materials has mainly focused on systems such as chalcogenides, phosphides, and heavy metal oxyhalides with an infrared transmission range greater than 3 μm. Among them, although heavy metal oxyhalide materials have a wide infrared transmission range and a high laser damage threshold, they usually have problems such as low nonlinear optical coefficient, easy deliquescence, and disordered crystal structure, making it difficult for them to become practical mid- and far-infrared nonlinear optical crystal materials. Therefore, chalcogenide and phosphide compounds with stable physical and chemical properties, wide transmission range, and large nonlinear optical coefficient are advantageous systems for developing high-performance mid- and far-infrared nonlinear optical materials. Currently, there are few varieties of commercially available mid- and far-infrared nonlinear optical crystal materials, and most of them are chalcopyrite chalcogenide (phosphide) materials developed around the 1970s, namely AgGaS2 (Q = S, Se; AGS / Se) and ZnGeP2 (ZGP), etc. With the rapid development of the laser field, the intrinsic performance defects of these materials, such as the low laser damage threshold in AGS / Se, the short infrared cut-off edge of ZGP, and the two-photon absorption near 1 μm, have restricted their wide application and cannot meet the current requirements for high-efficiency and high-power mid- and far-infrared laser output. Therefore, it is of great significance to develop new mid- and far-infrared nonlinear optical materials with balanced performance to replace existing crystals, and this is also one of the research hotspots in the current field of nonlinear optics. Summary of the Invention

[0003] The object of the present invention is to provide a compound sodium silver gallium sulfide, the general molecular formula of which is NaAg3Ga8S 14 , with a molecular weight of 1353.20 g / mol, having a crystal structure, an asymmetric center, and crystallizing in the Cm space group of the monoclinic system.

[0004] Another object of the present invention is to provide a sodium silver gallium sulfide infrared nonlinear optical crystal, the general molecular formula of which is NaAg3Ga8S 14 , with a molecular weight of 1353.20 g / mol, having an asymmetric center, crystallizing in the Cm space group of the monoclinic system, and the unit cell parameters are as follows: β = 114.981(2)°, Z = 2, and the volume is

[0005] Another object of the present invention is to provide a preparation method of a sodium silver gallium sulfide NaAg3Ga8S 14 infrared nonlinear optical crystal.

[0006] Another object of the present invention is to provide the use of a sodium silver gallium sulfide NaAg3Ga8S 14 infrared nonlinear optical crystal.

[0007] The compound sodium silver gallium sulfide described in the present invention has a molecular formula of NaAg3Ga8S 14 , with a molecular weight of 1353.20 g / mol, having a crystal structure, an asymmetric center, crystallizing in the Cm space group of the monoclinic system, and is prepared by the high-temperature solid-phase method.

[0008] The preparation method of the compound sodium silver gallium sulfide is prepared by the high-temperature solid-phase method, and the specific operation is carried out according to the following steps:

[0009] a. Mix the Na source material, Ag source material, Ga source material, and elemental S evenly according to the molar ratio of Na:Ag:Ga:S = 1:3:8:14, put them into a quartz glass tube with a diameter of Φ25 mm × 240 mm, and use a vacuum pump to evacuate the quartz tube to a vacuum degree of 10 -3 -10 -5 Pa for melting and sealing. The Na source material is metallic Na, Na2S, or NaI; the Ag source material is metallic Ag, Ag2S, or AgI; the Ga source material is metallic Ga or Ga2S3;

[0010] b. Put the sealed quartz tube in step a into a programmable temperature-controlled muffle furnace, heat it at a rate of 12 - 18 °C / h to 800 - 950 °C, carry out solid-phase reaction for 50 - 80 h, then cool it to 650 °C at a speed of 10 - 22 °C / h, turn off the furnace, take out the sample after natural cooling to room temperature, and crush and grind it to obtain a pure sample of powdered sodium silver gallium sulfide.

[0011] A sodium silver gallium sulfide infrared nonlinear optical crystal, the crystal formula of which is NaAg3Ga8S 14 , with a molecular weight of 1353.20 g / mol, having an asymmetric center, crystallizing in the Cm space group of the monoclinic system, and the unit cell parameters are: β = 114.981(2)°, Z = 2, and the volume is

[0012] The preparation method of the sodium silver gallium sulfide infrared nonlinear optical crystal described above is carried out by the high-temperature melt method, chemical vapor transport method or Bridgman method for crystal growth:

[0013] When growing the sodium silver gallium sulfide infrared nonlinear optical crystal by the high-temperature melt method, the specific operation is carried out according to the following steps:

[0014] a. According to the molar ratio of Na∶Ag∶Ga∶S = 1∶3∶8∶14, mix the Na source material, Ag source material, Ga source material and elemental S evenly, put them into a quartz glass tube with a diameter of Φ25mm×240mm, and use a vacuum pump to evacuate the quartz tube to a vacuum degree of 10 -3 -10 -5 Pa for melting and sealing, then put it into a programmable temperature-controlled muffle furnace, heat it at a rate of 12 - 18 °C / h to 800 - 950 °C, carry out solid-phase reaction for 50 - 80 h, then cool it to 650 °C at a speed of 10 - 22 °C / h, turn off the furnace, wait for it to cool naturally to room temperature, take out the sample, and crush and grind it to obtain a powdered pure sample of sodium silver gallium sulfide, where the Na source material is metallic Na, Na2S or NaI; the Ag source material is metallic Ag, Ag2S or AgI; the Ga source material is metallic Ga or Ga2S3;

[0015] b. Load the compound powder obtained in step a into a quartz tube, evacuate it to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, heat it at a rate of 10 - 18 °C / h to 900 - 1000 °C, keep it at a constant temperature for 60 - 100 h, and slowly cool it to room temperature at a rate of 2 - 8 °C / h. After the quartz tube cools, cut it open to obtain a pale yellow sodium silver gallium sulfide NaAg3Ga8S 14 infrared nonlinear optical crystal;

[0016] When growing the sodium silver gallium sulfide infrared nonlinear optical crystal by the chemical vapor transport method, the specific operation is carried out according to the following steps:

[0017] a. Mix the Na source material, Ag source material, Ga source material, and elemental S evenly according to the molar ratio of Na∶Ag∶Ga∶S = 1∶3∶8∶14, put them into a quartz glass tube with a diameter of Φ25mm×240mm, and use a vacuum pump to evacuate the quartz tube to a vacuum degree of 10 -3 -10 -5 Pa for melting and sealing, then put it into a programmable temperature-controlled muffle furnace, heat it at a rate of 12 - 18°C / h to 800 - 950°C, carry out a solid-phase reaction for 50 - 80h, then cool it to 650°C at a rate of 10 - 22°C / h and turn off the furnace. After natural cooling to room temperature, take out the sample, crush and grind it to obtain a powdery pure sample of sodium silver gallium sulfide. The Na source material is metallic Na, Na2S or NaI; the Ag source material is metallic Ag, Ag2S or AgI; the Ga source material is metallic Ga or Ga2S3;

[0018] b. Weigh the compound powder obtained in step a and iodine according to a ratio of 1:0.1 - 1, mix them evenly and put them into a quartz tube, evacuate it to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a tube furnace for chemical vapor transport at a high temperature zone of 850 - 950°C and a low temperature zone of 600 - 750°C, and grow sodium silver gallium sulfide crystals through a horizontal or vertical gradient temperature field. Heat it to 850 - 950°C in the high temperature zone and 650 - 750°C in the low temperature zone at a rate of 13 - 22°C / h simultaneously. The growth cycle is 18 - 36 days. After the growth is completed, slowly cool it to room temperature at a rate of 3 - 10°C / h, turn off the tube furnace. After the quartz tube cools, cut it open to obtain a pale yellow sodium silver gallium sulfide NaAg3Ga8S 14 infrared nonlinear optical crystal;

[0019] For growing sodium silver gallium sulfide infrared nonlinear optical crystals by the Bridgman method, the specific operation is carried out according to the following steps:

[0020] a. Mix the Na source material, Ag source material, Ga source material, and elemental S evenly according to the molar ratio of Na∶Ag∶Ga∶S = 1∶3∶8∶14, put them into a quartz glass tube with a diameter of Φ25mm×240mm, and use a vacuum pump to evacuate the quartz tube to a vacuum degree of 10 -3 -10 -5 Pa for melting and sealing, then put it into a programmable temperature-controlled muffle furnace, heat it at a rate of 12 - 18°C / h to 800 - 950°C, carry out a solid-phase reaction for 50 - 80h, then cool it to 650°C at a rate of 10 - 22°C / h and turn off the furnace. After natural cooling to room temperature, take out the sample, crush and grind it to obtain a powdery pure sample of sodium silver gallium sulfide. The Na source material is metallic Na, Na2S or NaI; the Ag source material is metallic Ag, Ag2S or AgI; the Ga source material is metallic Ga or Ga2S3;

[0021] b. Load the compound powder obtained in step a into a quartz tube with a diameter of Φ25mm×240mm, evacuate to 10 -3 Pa, then seal it with a hydrogen-oxygen flame, place it in a crucible lowering furnace, heat it to 870 - 980°C at a rate of 14 - 28°C / h, keep it at a constant temperature for 60 - 80h until the raw materials are completely melted, then lower the crucible lowering furnace vertically at a speed of 0.1 - 2.0mm / h, grow the sodium silver gallium sulfide crystal during the lowering process, the growth period is 20 - 32 days, after the crystal growth is completed, leave the crystal in the crucible lowering furnace for annealing, and cool it to room temperature at a rate of 18 - 30°C / h to obtain a pale yellow sodium silver gallium sulfide NaAg3Ga8S 14 infrared nonlinear optical crystal.

[0022] Use of the sodium silver gallium sulfide infrared nonlinear optical crystal in the preparation of infrared band laser frequency conversion crystals, infrared lasers, infrared communication devices or infrared laser guidance devices.

[0023] A compound sodium silver gallium sulfide NaAg3Ga8S according to the present invention 14 is prepared according to the following chemical reaction formula:

[0024] (1) Na + 3Ag + 8Ga + 14S = NaAg3Ga8S 14 ;

[0025] (2) 0.5Na₂S + 3Ag + 8Ga + 13.5S = NaAg3Ga8S 14 ;

[0026] (3) NaI + 3Ag + 8Ga + 14S = NaAg3Ga8S 14 + 0.5I₂;

[0027] (4) Na + 1.5Ag₂S + 8Ga + 12.5S = NaAg3Ga8S 14 ;

[0028] (5) Na + 3AgI + 8Ga + 14S = NaAg3Ga8S 14 + 1.5I₂;

[0029] (6) Na + 3Ag + 4Ga₂S₃ + 2S = NaAg3Ga8S 14 ;

[0030] (7) 0.5Na₂S + 3Ag + 4Ga₂S₃ + 1.5S = NaAg3Ga8S 14 ;

[0031] (8) NaI + 3Ag + 4Ga₂S₃ + 2S = NaAg3Ga8S 14+0.5I2;

[0032] (9)Na + 1.5Ag2S + 4Ga2S3 + 0.5S = NaAg3Ga8S 14 ;

[0033] (10)Na + 3AgI + 4Ga2S3 + 2S = NaAg3Ga8S 14 +1.5I2;

[0034] The preparation method of a sodium silver gallium sulfide nonlinear optical crystal according to the present invention can obtain NaAg3Ga8S with a centimeter-scale size 14 infrared nonlinear optical crystal; by using a large-sized crucible and extending the growth time, a correspondingly larger-sized NaAg3Ga8S 14 infrared nonlinear optical crystal can be obtained.

[0035] A sodium silver gallium sulfide NaAg3Ga8S 14 infrared nonlinear optical crystal according to the present invention has the advantages of relatively low synthesis temperature, no inclusions, low cost, and easy access to larger-sized crystals; the obtained sodium silver gallium sulfide NaAg3Ga8S 14 infrared nonlinear optical crystal and device also have the advantages of strong laser damage resistance, large nonlinear optical effect, wide light transmission band, high hardness, good mechanical properties, not easy to break and deliquesce, easy to process and preserve, etc.; this crystal can be used to fabricate infrared nonlinear optical devices.

[0036] According to the crystallographic data of the crystal, the crystal blank is oriented, the crystal is cut according to the required angle, thickness and cross-sectional size, and the light-transmitting surface of the crystal is polished, then it can be used as a nonlinear optical device.

[0037] The sodium silver gallium sulfide NaAg3Ga8S 14 infrared nonlinear optical crystal is used in the preparation of infrared band laser frequency conversion crystals, infrared lasers, infrared electro-optic devices, infrared communication devices or infrared laser guidance devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 is a schematic structural diagram of sodium silver gallium sulfide NaAg3Ga8S of the present invention 14 : Ag and Ga atoms coordinate with S atoms in the crystal structure to obtain [AgS4] and [GaS4] groups, while Na atoms coordinate with S atoms in the crystal structure to obtain [NaS8] groups ( Figure 1 a). Subsequently, three [AgS4] tetrahedral groups are connected in a corner-sharing manner to form an [Ag3S 10trimers, and six [GaS4] tetrahedral groups are interconnected by sharing S atoms at the corners to form a [Ga6S8] dodecagonal ring ( Figure 1 b). Isolated [Ag3S 10 trimers perpendicular to the b-axis are filled in the central pores of the three-dimensional [Ga6S8] ∞ framework composed of [Ga6S8] dodecagonal rings ( Figure 1 c-1d), constructing a three-dimensional diamond-like anion framework. In addition, the [NaS8] polyhedral group is located in the pores of the three-dimensional diamond-like anion framework to balance the valence state, and finally forms a three-dimensional pore-like crystal structure of NaAg3Ga8S 14 ( Figure 1 e-1f).

[0039] Figure 2 is the comparison chart of the experimental value and the theoretical value of the X-ray diffraction of the polycrystalline powder of the sodium silver gallium sulfide NaAg3Ga8S crystal of the present invention 14 .

[0040] Figure 3 is the schematic diagram of the second-order nonlinear optical effect signal of the sodium silver gallium sulfide NaAg3Ga8S crystal of the present invention. In the particle size range of 180-220 μm, NaAg3Ga8S 14 exhibits a large NLO response, about 0.7 times that of the reference AgGaS2 14 .

[0041] Figure 4 is the working principle diagram of the optical device of the present invention, where 1 is a laser, 2 is a convex lens, 3 is the NaAg3Ga8S 14 infrared nonlinear optical crystal after crystal post-treatment and optical processing, 4 is a prism, and 5 is a filter Specific Embodiments

[0042] Any feature disclosed in this specification, unless specifically stated, can be replaced by other equivalent or similar-purpose alternative features. Unless specifically stated, each feature is only an example in 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 of the present invention

[0043] The present invention will be further described in detail below with reference to the drawings and specific embodiments

[0044] Example 1

[0045] Using the chemical reaction formula Na + 3Ag + 8Ga + 14S = NaAg3Ga8S 14 , the compound NaAg3Ga8S 14 is prepared by the high-temperature solid-phase method. The specific operation is carried out according to the following steps

[0046] After uniformly mixing 0.085 g of metallic element Na, 1.196 g of metallic element Ag, 2.061 g of metallic element Ga and 1.658 g of elemental S, put them into a quartz glass tube with Φ25mm×240mm, and use a vacuum pump to evacuate the quartz tube to a vacuum degree of 10 -3 -10 - 5 Pa and then carry out melting and sealing;

[0047] Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it to 850 °C at a rate of 17 °C / h, carry out solid-phase reaction for 55 h, then cool it to 650 °C at a speed of 16 °C / h and turn off the furnace. After naturally cooling to room temperature, take out the sample and crush and grind it to obtain powdery NaAg3Ga8S 14 compound.

[0048] Example 2

[0049] Using the chemical reaction formula 0.5Na2S + 3Ag + 8Ga + 13.5S = NaAg3Ga8S 14 , prepare the compound NaAg3Ga8S by the high-temperature solid-phase method 14 , and the specific operation is carried out according to the following steps:

[0050] After uniformly mixing 0.144 g of Na2S, 1.196 g of metallic element Ag, 2.061 g of metallic element Ga and 1.599 g of elemental S, put them into a quartz glass tube with Φ25mm×240mm, and use a vacuum pump to evacuate the quartz tube to a vacuum degree of 10 -3 -10 -5 Pa and then carry out melting and sealing;

[0051] Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it to 800 °C at a rate of 12 °C / h, carry out solid-phase reaction for 60 h, then cool it to 650 °C at a speed of 18 °C / h and turn off the furnace. After naturally cooling to room temperature, take out the sample and crush and grind it to obtain powdery NaAg3Ga8S 14 compound.

[0052] Example 3

[0053] Using the chemical reaction formula NaI + 3Ag + 8Ga + 14S = NaAg3Ga8S 14 +0.5I2, prepare the compound NaAg3Ga8S by the high-temperature solid-phase method 14 , and the specific operation is carried out according to the following steps:

[0054] 0.506 g of NaI, 1.093 g of metallic element Ag, 1.884 g of metallic element Ga and 1.516 g of metallic element S were mixed evenly and placed in a Φ25 mm × 240 mm quartz glass tube. The quartz tube was evacuated to a vacuum degree of 10 -3 -10 -5 After Pa, melt sealing is performed;

[0055] The sealed quartz tube was placed in a programmable temperature-controlled muffle furnace and heated to 900°C at a rate of 15°C / h for solid-phase reaction for 70h. The temperature was then cooled to 650°C at a rate of 15°C / h and the furnace was turned off. After cooling naturally to room temperature, the sample was taken out and crushed to obtain powdered NaAg3Ga8S 14 compound.

[0056] Example 4

[0057] According to the chemical reaction formula Na+1.5Ag2S+8Ga+12.5S=NaAg3Ga8S 14 , the compound NaAg3Ga8S was prepared by high temperature solid phase method 14 , the specific operations are as follows:

[0058] 0.085 g of metallic elemental Na, 1.373 g of Ag2S, 2.061 g of metallic elemental Ga and 1.481 g of elemental S were mixed evenly and placed in a Φ25 mm × 240 mm quartz glass tube. The quartz tube was evacuated to a vacuum degree of 10 -3 -10 -5 After Pa, melt sealing is performed;

[0059] The sealed quartz tube was placed in a programmable temperature-controlled muffle furnace and heated to 920°C at a rate of 13°C / h for solid-phase reaction for 75h. The temperature was then cooled to 650°C at a rate of 20°C / h and the furnace was turned off. After cooling naturally to room temperature, the sample was taken out and crushed to obtain powdered NaAg3Ga8S 14 compound.

[0060] Example 5

[0061] According to the chemical reaction formula Na+3AgI+8Ga+14S=NaAg3Ga8S 14 +1.5I2, using high temperature solid phase method to prepare compound NaAg3Ga8S 14 , the specific operations are as follows:

[0062] 0.066 g of metallic element Na, 2.031 g of AgI, 1.608 g of metallic element Ga and 1.294 g of metallic element S were mixed evenly and placed in a Φ25 mm × 240 mm quartz glass tube. The quartz tube was evacuated to a vacuum degree of 10-3 -10 -5 After reaching 10 Pa, perform melting and sealing;

[0063] Put the sealed quartz tube into a muffle furnace with programmable temperature control, heat it to 880 °C at a rate of 18 °C / h, carry out solid-phase reaction for 70 h, then cool it to 650 °C at a rate of 17 °C / h, turn off the furnace, wait for it to cool naturally to room temperature, take out the sample, and crush and grind it to obtain powdery NaAg3Ga8S 14 compound.

[0064] Example 6

[0065] Using the chemical reaction formula Na + 3Ag + 4Ga2S3 + 2S = NaAg3Ga8S 14 Prepare the compound NaAg3Ga8S by the high-temperature solid-phase method 14 , and the specific operation is carried out according to the following steps:

[0066] Mix 0.085 g of metallic sodium, 1.196 g of metallic silver, 3.483 g of Ga2S3 and 0.237 g of elemental sulfur evenly, put them into a quartz glass tube with Φ25 mm × 240 mm, and use a vacuum pump to pump the quartz tube to a vacuum degree of 10 -3 -10 -5 Pa, then perform melting and sealing;

[0067] Put the sealed quartz tube into a muffle furnace with programmable temperature control, heat it to 930 °C at a rate of 15 °C / h, carry out solid-phase reaction for 80 h, then cool it to 650 °C at a rate of 11 °C / h, turn off the furnace, wait for it to cool naturally to room temperature, take out the sample, and crush and grind it to obtain powdery NaAg3Ga8S 14 compound.

[0068] Example 7

[0069] Using the chemical reaction formula 0.5Na2S + 3Ag + 4Ga2S3 + 1.5S = NaAg3Ga8S 14 Prepare the compound NaAg3Ga8S by the high-temperature solid-phase method 14 , and the specific operation is carried out according to the following steps:

[0070] Mix 0.144 g of Na2S, 1.196 g of metallic silver, 3.483 g of Ga2S3 and 0.178 g of elemental sulfur evenly, put them into a quartz glass tube with Φ25 mm × 240 mm, and use a vacuum pump to pump the quartz tube to a vacuum degree of 10 -3 -10 -5 Pa, then perform melting and sealing;

[0071] Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it to 830 °C at a rate of 16 °C / h, carry out solid-phase reaction for 80 h, then cool it to 650 °C at a rate of 22 °C / h, turn off the furnace, wait for it to cool naturally to room temperature, take out the sample, and crush and grind it to obtain powdery NaAg3Ga8S 14 compound.

[0072] Example 8

[0073] According to the chemical reaction formula NaI + 3Ag + 4Ga2S3 + 2S = NaAg3Ga8S 14 + 0.5I2, prepare the compound NaAg3Ga8S by the high-temperature solid-phase method 14 , and the specific operation is carried out according to the following steps:

[0074] Mix 0.506 g of NaI, 1.093 g of metallic Ag, 3.184 g of Ga2S3 and 0.217 g of elemental S evenly, put them into a quartz glass tube with Φ25 mm × 240 mm, and use a vacuum pump to pump the quartz tube to a vacuum degree of 10 -3 -10 -5 Pa and then carry out melting and sealing;

[0075] Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it to 890 °C at a rate of 17 °C / h, carry out solid-phase reaction for 55 h, then cool it to 650 °C at a rate of 20 °C / h, turn off the furnace, wait for it to cool naturally to room temperature, take out the sample, and crush and grind it to obtain powdery NaAg3Ga8S 14 compound.

[0076] Example 9

[0077] According to the chemical reaction formula Na + 1.5Ag2S + 4Ga2S3 + 0.5S = NaAg3Ga8S 14 , prepare the compound NaAg3Ga8S by the high-temperature solid-phase method 14 , and the specific operation is carried out according to the following steps:

[0078] Mix 0.085 g of metallic Na, 1.373 g of Ag2S, 3.483 g of Ga2S3 and 0.059 g of elemental S evenly, put them into a quartz glass tube with Φ25 mm × 240 mm, and use a vacuum pump to pump the quartz tube to a vacuum degree of 10 -3 -10 -5 Pa and then carry out melting and sealing;

[0079] Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it to 870 °C at a rate of 15 °C / h, carry out solid-phase reaction for 75 h, then cool it to 650 °C at a rate of 22 °C / h, turn off the furnace, wait for it to cool naturally to room temperature, take out the sample, and crush and grind it to obtain powdered NaAg3Ga8S 14 compound.

[0080] Example 10

[0081] Using the chemical reaction formula Na + 3AgI + 4Ga2S3 + 2S = NaAg3Ga8S 14 + 1.5I2, prepare the compound NaAg3Ga8S by the high-temperature solid-phase method 14 , and the specific operation is carried out according to the following steps:

[0082] Mix 0.066 g of metallic sodium, 2.031 g of AgI, 2.718 g of Ga2S3 and 0.185 g of elemental sulfur evenly, put them into a quartz glass tube with Φ25mm×240mm, and use a vacuum pump to pump the quartz tube to a vacuum degree of 10 -3 -10 -5 Pa and then carry out melting and sealing;

[0083] Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it to 950 °C at a rate of 18 °C / h, carry out solid-phase reaction for 50 h, then cool it to 650 °C at a rate of 11 °C / h, turn off the furnace, wait for it to cool naturally to room temperature, take out the sample, and crush and grind it to obtain powdered NaAg3Ga8S 14 compound.

[0084] Example 11

[0085] The growth of NaAg3Ga8S 14 infrared nonlinear optical crystal by the high-temperature melt method is carried out according to the following steps:

[0086] Put the pure powdered sample of NaAg3Ga8S obtained in Example 1 into a quartz tube with Φ25mm×240mm, evacuate to 10 14 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, heat it to 900 °C at a rate of 17 °C / h, keep it at a constant temperature for 70 h, then slowly cool it to room temperature at a rate of 3 °C / h, turn off the muffle furnace, cut it open after the quartz tube cools, and obtain a pale yellow NaAg3Ga8S with a size of Φ3.2mm×4.5mm -3 infrared nonlinear optical crystal. 14 Example 12

[0087] The growth of NaAg3Ga8S

[0088] by the high-temperature melt method 14Infrared nonlinear optical crystal, and the specific operation is carried out according to the following steps:

[0089] Load the pure NaAg3Ga8S powder sample obtained in Example 2 14 into a quartz glass tube with a diameter of Φ25mm×240mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, heat it to 920°C at a rate of 16°C / h, keep it at a constant temperature for 65h; then slowly cool it to room temperature at a rate of 7°C / h, turn off the muffle furnace, cut it open after the quartz tube cools down, and obtain a pale yellow NaAg3Ga8S 14 infrared nonlinear optical crystal with a size of Φ5.4mm×3.6mm.

[0090] Example 13

[0091] For growing the NaAg3Ga8S 14 infrared nonlinear optical crystal by the high-temperature melt method, the specific operation is carried out according to the following steps:

[0092] Load the pure NaAg3Ga8S powder sample obtained in Example 3 14 into a quartz glass tube with a diameter of Φ25mm×240mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, heat it to 960°C at a rate of 15°C / h, keep it at a constant temperature for 85h; then slowly cool it to room temperature at a rate of 3°C / h, turn off the muffle furnace, cut it open after the quartz tube cools down, and obtain a pale yellow NaAg3Ga8S 14 infrared nonlinear optical crystal with a size of Φ3.2mm×2.4mm.

[0093] Example 14

[0094] For growing the NaAg3Ga8S 14 infrared nonlinear optical crystal by the high-temperature melt method, the specific operation is carried out according to the following steps:

[0095] Load the pure NaAg3Ga8S powder sample obtained in Example 4 14 into a quartz glass tube with a diameter of Φ25mm×240mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, heat it to 940°C at a rate of 12°C / h, keep it at a constant temperature for 90h; then slowly cool it to room temperature at a rate of 4°C / h, turn off the muffle furnace, cut it open after the quartz tube cools down, and obtain a pale yellow NaAg3Ga8S 14 infrared nonlinear optical crystal with a size of Φ4.5mm×3.2mm.

[0096] Example 15

[0097] For growing the NaAg3Ga8S 14Infrared nonlinear optical crystal, and the specific operation is carried out according to the following steps:

[0098] Load the pure NaAg3Ga8S powder sample obtained in Example 5 14 into a quartz glass tube with a diameter of Φ25mm×240mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, heat it to 910°C at a rate of 13°C / h, keep it at a constant temperature for 80h; then slowly cool it to room temperature at a rate of 6°C / h, turn off the muffle furnace, and cut it open after the quartz tube cools down to obtain a light yellow NaAg3Ga8S 14 infrared nonlinear optical crystal with a size of Φ3.7mm×2.6mm.

[0099] Example 16

[0100] Growing NaAg3Ga8S 14 infrared nonlinear optical crystal by the high-temperature melt method, and the specific operation is carried out according to the following steps:

[0101] Load the pure NaAg3Ga8S powder sample obtained in Example 6 14 into a quartz glass tube with a diameter of Φ25mm×240mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, heat it to 930°C at a rate of 18°C / h, keep it at a constant temperature for 90h; then slowly cool it to room temperature at a rate of 8°C / h, turn off the muffle furnace, and cut it open after the quartz tube cools down to obtain a light yellow NaAg3Ga8S 14 infrared nonlinear optical crystal with a size of Φ2.2mm×1.8mm.

[0102] Example 17

[0103] Growing NaAg3Ga8S 14 infrared nonlinear optical crystal by the high-temperature melt method, and the specific operation is carried out according to the following steps:

[0104] Load the pure NaAg3Ga8S powder sample obtained in Example 7 14 into a quartz glass tube with a diameter of Φ25mm×240mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, heat it to 980°C at a rate of 14°C / h, keep it at a constant temperature for 85h; then slowly cool it to room temperature at a rate of 5°C / h, turn off the muffle furnace, and cut it open after the quartz tube cools down to obtain a light yellow NaAg3Ga8S 14 infrared nonlinear optical crystal with a size of Φ3.6mm×2.8mm.

[0105] Example 18

[0106] Growing NaAg3Ga8S 14Infrared nonlinear optical crystal, the specific operation is carried out according to the following steps:

[0107] Load the pure NaAg3Ga8S powder sample obtained in Example 8 14 into a quartz glass tube with a diameter of Φ25mm×240mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, heat it to 1000 °C at a rate of 10 °C / h, keep it at a constant temperature for 95 h; then slowly cool it to room temperature at a rate of 2 °C / h, turn off the muffle furnace, cut it open after the quartz tube cools down, and obtain a light yellow NaAg3Ga8S infrared nonlinear optical crystal with a size of Φ4.6mm×3.7mm. 14 Infrared nonlinear optical crystal.

[0108] Example 19

[0109] The growth of NaAg3Ga8S infrared nonlinear optical crystal by the high-temperature melt method 14 is carried out according to the following steps:

[0110] Load the pure NaAg3Ga8S powder sample obtained in Example 9 14 into a quartz glass tube with a diameter of Φ25mm×240mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, heat it to 950 °C at a rate of 16 °C / h, keep it at a constant temperature for 60 h; then slowly cool it to room temperature at a rate of 7 °C / h, turn off the muffle furnace, cut it open after the quartz tube cools down, and obtain a light yellow NaAg3Ga8S infrared nonlinear optical crystal with a size of Φ3.1mm×2.3mm. 14 Infrared nonlinear optical crystal.

[0111] Example 20

[0112] The growth of NaAg3Ga8S infrared nonlinear optical crystal by the high-temperature melt method 14 is carried out according to the following steps:

[0113] Load the pure NaAg3Ga8S powder sample obtained in Example 10 14 into a quartz glass tube with a diameter of Φ25mm×240mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, heat it to 970 °C at a rate of 11 °C / h, keep it at a constant temperature for 75 h; then slowly cool it to room temperature at a rate of 4 °C / h, turn off the muffle furnace, cut it open after the quartz tube cools down, and obtain a light yellow NaAg3Ga8S infrared nonlinear optical crystal with a size of Φ6.0mm×4.4mm. 14 Infrared nonlinear optical crystal.

[0114] Example 21

[0115] The growth of NaAg3Ga8S by chemical vapor transport method14 Infrared nonlinear optical crystal, and the specific operation is carried out according to the following steps:

[0116] Weigh the pure NaAg3Ga8S powder sample obtained in Example 1 and iodine in a ratio of 1:0.1, then load them into a quartz tube with a diameter of Φ25mm×240mm, evacuate to 10 14 Pa, seal it with a hydrogen-oxygen flame, place it in a tube-type growth furnace, and carry out chemical vapor transport at a high-temperature zone of 900°C and a low-temperature zone of 620°C. Through a horizontal gradient temperature field, crystal growth of NaAg3Ga8S -3 is carried out; simultaneously heat it to 900°C in the high-temperature zone and 620°C in the low-temperature zone at a rate of 15°C / h, with a growth period of 25 days. After the growth is completed, slowly cool it to room temperature at a rate of 4°C / h, turn off the tube-type growth furnace, cut it open after the quartz tube cools, and obtain a light yellow NaAg3Ga8S 144 infrared nonlinear optical crystal with a size of Φ4.4mm×2.8mm at the low-temperature end. 14

[0117] Example 22

[0118] Growing NaAg3Ga8S 14 infrared nonlinear optical crystal by chemical vapor transport method, and the specific operation is carried out according to the following steps:

[0119] Weigh the pure NaAg3Ga8S powder sample obtained in Example 2 and iodine in a ratio of 1:0.3, then load them into a quartz tube with a diameter of Φ25mm×240mm, evacuate to 10 14 Pa, seal it with a hydrogen-oxygen flame, place it in a tube-type growth furnace, and carry out chemical vapor transport at a high-temperature zone of 880°C and a low-temperature zone of 610°C. Through a horizontal gradient temperature field, crystal growth of NaAg3Ga8S -3 is carried out; simultaneously heat it to 880°C in the high-temperature zone and 610°C in the low-temperature zone at a rate of 14°C / h, with a growth period of 21 days. After the growth is completed, slowly cool it to room temperature at a rate of 9°C / h, turn off the tube-type growth furnace, cut it open after the quartz tube cools, and obtain a light yellow NaAg3Ga8S 14 infrared nonlinear optical crystal with a size of Φ3.8mm×2.6mm at the low-temperature end. 14

[0120] Example 23

[0121] Growing NaAg3Ga8S 14 infrared nonlinear optical crystal by chemical vapor transport method, and the specific operation is carried out according to the following steps:

[0122] Weigh the pure NaAg3Ga8S powder sample obtained in Example 3 14 ​​The pure powder sample and iodine are weighed according to a ratio of 1:0.5 and then loaded into a quartz tube with a diameter of Φ25mm×240mm. After evacuating to 10 -3 Pa, it is sealed with a hydrogen-oxygen flame and placed in a tube furnace for chemical vapor transport at a high-temperature zone of 920°C and a low-temperature zone of 670°C. The crystal growth of NaAg3Ga8S 14 is carried out through a horizontal gradient temperature field; it is heated to 920°C in the high-temperature zone and 670°C in the low-temperature zone at a rate of 16°C / h simultaneously. The growth period is 18 days. After the growth is completed, it is slowly cooled to room temperature at a rate of 3°C / h, the tube furnace is turned off, and after the quartz tube cools, it is cut open to obtain a light yellow NaAg3Ga8S 14 infrared nonlinear optical crystal with a size of Φ4.2mm×3.3mm at the low-temperature end.

[0123] Example 24

[0124] The growth of the NaAg3Ga8S 14 infrared nonlinear optical crystal by the chemical vapor transport method is specifically carried out according to the following steps:

[0125] The pure powder sample of NaAg3Ga8S obtained in Example 4 14 and iodine are weighed according to a ratio of 1:0.7 and then loaded into a quartz tube with a diameter of Φ25mm×240mm. After evacuating to 10 -3 Pa, it is sealed with a hydrogen-oxygen flame and placed in a tube furnace for chemical vapor transport at a high-temperature zone of 940°C and a low-temperature zone of 700°C. The crystal growth of NaAg3Ga8S 14 is carried out through a horizontal gradient temperature field; it is heated to 940°C in the high-temperature zone and 700°C in the low-temperature zone at a rate of 13°C / h simultaneously. The growth period is 30 days. After the growth is completed, it is slowly cooled to room temperature at a rate of 8°C / h, the tube furnace is turned off, and after the quartz tube cools, it is cut open to obtain a light yellow NaAg3Ga8S 14 infrared nonlinear optical crystal with a size of Φ4.3mm×3.5mm at the low-temperature end.

[0126] Example 25

[0127] The growth of the NaAg3Ga8S 14 infrared nonlinear optical crystal by the chemical vapor transport method is specifically carried out according to the following steps:

[0128] The pure powder sample of NaAg3Ga8S obtained in Example 5 14 and iodine are weighed according to a ratio of 1:0.9 and then loaded into a quartz tube with a diameter of Φ25mm×240mm. After evacuating to 10 -3 Pa, it is sealed with a hydrogen-oxygen flame and placed in a tube furnace for chemical vapor transport at a high-temperature zone of 850°C and a low-temperature zone of 650°C. The chemical vapor transport of NaAg3Ga8S is carried out through a horizontal gradient temperature field.14 Crystal growth; simultaneously heating to 850 °C in the high-temperature zone and 650 °C in the low-temperature zone at a rate of 20 °C / h, with a growth period of 32 days. After growth, slowly cool to room temperature at a rate of 5 °C / h, turn off the tube furnace, and cut it after the quartz tube cools. A pale yellow NaAg3Ga8S with a size of Φ5.1 mm × 3.8 mm is obtained at the low-temperature end 14 Infrared nonlinear optical crystal

[0129] Example 26

[0130] Growing NaAg3Ga8S by chemical vapor transport method 14 Infrared nonlinear optical crystal, and the specific operation is carried out according to the following steps:

[0131] Take the pure NaAg3Ga8S powder obtained in Example 6 14 Weigh the pure sample powder and iodine in a ratio of 1:0.2 and put them into a quartz tube with a size of Φ25 mm × 240 mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a tube furnace, and carry out chemical vapor transport at 870 °C in the high-temperature zone and 680 °C in the low-temperature zone. Grow the crystal of NaAg3Ga8S through a horizontal gradient temperature field 14 Crystal growth; simultaneously heating to 870 °C in the high-temperature zone and 680 °C in the low-temperature zone at a rate of 17 °C / h, with a growth period of 19 days. After growth, slowly cool to room temperature at a rate of � °C / h, turn off the tube furnace, and cut it after the quartz tube cools. A pale yellow NaAg3Ga8S with a size of Φ3.6 mm × 2.9 mm is obtained at the low-temperature end 14 Infrared nonlinear optical crystal

[0132] Example 27

[0133] Growing NaAg3Ga8S by chemical vapor transport method 14 Infrared nonlinear optical crystal, and the specific operation is carried out according to the following steps:

[0134] Take the pure NaAg3Ga8S powder obtained in Example 7 14 Weigh the pure sample powder and iodine in a ratio of 1:0.4 and put them into a quartz tube with a size of Φ25 mm × 240 mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a tube furnace, and carry out chemical vapor transport at 890 °C in the high-temperature zone and 700 °C in the low-temperature zone. Grow the crystal of NaAg3Ga8S through a horizontal gradient temperature field 14Crystal growth; simultaneously heating to 890 °C in the high-temperature zone and 700 °C in the low-temperature zone at a rate of 22 °C / h, with a growth period of 18 days. After growth, slowly cool to room temperature at a rate of 4 °C / h, turn off the tube furnace. After the quartz tube cools, cut it open to obtain light yellow NaAg3Ga8S with a size of Φ5.5 mm × 3.6 mm at the low-temperature end. 14 Infrared nonlinear optical crystal.

[0135] Example 28

[0136] The growth of NaAg3Ga8S by chemical vapor transport method 14 Infrared nonlinear optical crystal, and the specific operation is carried out according to the following steps:

[0137] Take the pure NaAg3Ga8S powder sample obtained in Example 8 14 and iodine in a ratio of 1:0.6 by weight, put them into a quartz tube with a size of Φ25 mm × 240 mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a tube furnace for chemical vapor transport at 950 °C in the high-temperature zone and 750 °C in the low-temperature zone, and carry out the crystal growth of NaAg3Ga8S 14 through a horizontal gradient temperature field; simultaneously heat to 950 °C in the high-temperature zone and 750 °C in the low-temperature zone at a rate of 15 °C / h, with a growth period of 36 days. After growth, slowly cool to room temperature at a rate of 3 °C / h, turn off the tube furnace. After the quartz tube cools, cut it open to obtain light yellow NaAg3Ga8S with a size of Φ6.2 mm × 4.8 mm at the low-temperature end. 14 Infrared nonlinear optical crystal.

[0138] Example 29

[0139] The growth of NaAg3Ga8S by chemical vapor transport method 14 Infrared nonlinear optical crystal, and the specific operation is carried out according to the following steps:

[0140] Take the pure NaAg3Ga8S powder sample obtained in Example 9 14 and iodine in a ratio of 1:0.8 by weight, put them into a quartz tube with a size of Φ25 mm × 240 mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a tube furnace for chemical vapor transport at 930 °C in the high-temperature zone and 690 °C in the low-temperature zone, and carry out the crystal growth of NaAg3Ga8S 14 through a horizontal gradient temperature field; simultaneously heat to 930 °C in the high-temperature zone and 690 °C in the low-temperature zone at a rate of 19 °C / h, with a growth period of 21 days. After growth, slowly cool to room temperature at a rate of 7 °C / h, turn off the tube furnace. After the quartz tube cools, cut it open to obtain light yellow NaAg3Ga8S with a size of Φ3.8 mm × 2.6 mm at the low-temperature end.14 Infrared nonlinear optical crystal.

[0141] Example 30

[0142] The growth of NaAg3Ga8S by chemical vapor transport method 14 Infrared nonlinear optical crystal, and the specific operation is carried out according to the following steps:

[0143] Weigh the pure NaAg3Ga8S powder obtained in Example 10 and iodine in a ratio of 1:1.0, then load them into a quartz tube with a diameter of Φ25mm×240mm, evacuate to 10 14 Pa, seal it with a hydrogen-oxygen flame, place it in a tube furnace, and perform chemical vapor transport at a high temperature zone of 910°C and a low temperature zone of 710°C. The crystal growth of NaAg3Ga8S is carried out through a horizontal gradient temperature field; simultaneously heat up to 910°C in the high temperature zone and 710°C in the low temperature zone at a rate of 17°C / h, the growth period is 30 days, after the growth is completed, slowly cool down to room temperature at a rate of 6°C / h, turn off the tube furnace, cut it after the quartz tube cools down, and obtain a light yellow NaAg3Ga8S -3 Infrared nonlinear optical crystal with a size of Φ4.5mm×3.6mm at the low temperature end. 14 Infrared nonlinear optical crystal. 14 Infrared nonlinear optical crystal.

[0144] Example 31

[0145] The growth of NaAg3Ga8S by the Bridgman method 14 Infrared nonlinear optical crystal, and the specific operation is carried out according to the following steps:

[0146] Load the pure NaAg3Ga8S powder obtained in Example 1 into a quartz tube with a diameter of Φ25mm×240mm, evacuate to 10 14 Pa, seal it with a hydrogen-oxygen flame, place it in a Bridgman furnace, heat up to 890°C at a rate of 18°C / h, keep it at a constant temperature for 60h until the raw materials are completely melted, then lower the crucible in the Bridgman furnace vertically at a speed of 1.5mm / h, and carry out the crystal growth of NaAg3Ga8S -3 during the lowering process. The growth period is 24 days. After the crystal growth is completed, anneal the crystal in the Bridgman furnace and cool it down to room temperature at a rate of 23°C / h, then obtain a light yellow NaAg3Ga8S 14 Infrared nonlinear optical crystal with a size of Φ3.6mm×2.5mm. 14 Infrared nonlinear optical crystal.

[0147] Example 32

[0148] The growth of NaAg3Ga8S by the Bridgman method 14 Infrared nonlinear optical crystal, and the specific operation is carried out according to the following steps:

[0149] The pure NaAg3Ga8S powder sample obtained in Example 2 14 was loaded into a quartz tube with a diameter of Φ25mm×240mm, evacuated to 10 -3 Pa and then sealed with a hydrogen-oxygen flame. It was placed in a crucible-lowering furnace and heated to 910℃ at a rate of 16℃ / h. After maintaining a constant temperature for 65h until the raw materials were completely melted, the crucible-lowering furnace was vertically lowered at a speed of 1.0mm / h. During the lowering process, NaAg3Ga8S 14 crystal growth was carried out. The growth cycle was 26 days. After the crystal growth was completed, the crystal was left in the crucible-lowering furnace for annealing and cooled to room temperature at a rate of 25℃ / h, thus obtaining a light yellow NaAg3Ga8S 14 infrared nonlinear optical crystal with a size of Φ3.3mm×2.4mm.

[0150] Example 33

[0151] The growth of NaAg3Ga8S 14 infrared nonlinear optical crystal by the crucible-lowering method was carried out according to the following steps:

[0152] The pure NaAg3Ga8S powder sample obtained in Example 3 14 was loaded into a quartz tube with a diameter of Φ25mm×240mm, evacuated to 10 -3 Pa and then sealed with a hydrogen-oxygen flame. It was placed in a crucible-lowering furnace and heated to 980℃ at a rate of 14℃ / h. After maintaining a constant temperature for 75h until the raw materials were completely melted, the crucible-lowering furnace was vertically lowered at a speed of 1.2mm / h. During the lowering process, NaAg3Ga8S 14 crystal growth was carried out. The growth cycle was 28 days. After the crystal growth was completed, the crystal was left in the crucible-lowering furnace for annealing and cooled to room temperature at a rate of 28℃ / h, thus obtaining a light yellow NaAg3Ga8S 14 infrared nonlinear optical crystal with a size of Φ4.8mm×3.6mm.

[0153] Example 34

[0154] The growth of NaAg3Ga8S 14 infrared nonlinear optical crystal by the crucible-lowering method was carried out according to the following steps:

[0155] The pure NaAg3Ga8S powder sample obtained in Example 4 14 was loaded into a quartz tube with a diameter of Φ25mm×240mm, evacuated to 10 -3 Pa and then sealed with a hydrogen-oxygen flame. It was placed in a crucible-lowering furnace and heated to 870℃ at a rate of 26℃ / h. After maintaining a constant temperature for 60h until the raw materials were completely melted, the crucible-lowering furnace was vertically lowered at a speed of 0.5mm / h. During the lowering process, NaAg3Ga8S14 Crystal growth was carried out with a growth period of 30 days. After the crystal growth was completed, the crystal was left in the Bridgman furnace for annealing and cooled to room temperature at a rate of 30 °C / h, thus obtaining a pale yellow NaAg3Ga8S infrared nonlinear optical crystal with dimensions of Φ3.2 mm × 2.6 mm. 14 Infrared nonlinear optical crystal.

[0156] Example 35

[0157] The growth of NaAg3Ga8S by the Bridgman method 14 Infrared nonlinear optical crystal, and the specific operation is carried out according to the following steps:

[0158] The pure NaAg3Ga8S powder obtained in Example 5 14 was loaded into a quartz tube with dimensions of Φ25 mm × 240 mm, evacuated to 10 -3 Pa and then sealed with a hydrogen-oxygen flame. It was placed in a Bridgman furnace and heated to 970 °C at a rate of 15 °C / h. After maintaining the temperature for 70 h until the raw materials were completely melted, the Bridgman furnace was vertically lowered at a speed of 1.8 mm / h. During the lowering process, the growth of NaAg3Ga8S 14 crystal was carried out with a growth period of 22 days. After the crystal growth was completed, the crystal was left in the Bridgman furnace for annealing and cooled to room temperature at a rate of 18 °C / h, thus obtaining a pale yellow NaAg3Ga8S infrared nonlinear optical crystal with dimensions of Φ4.0 mm × 3.2 mm. 14 Infrared nonlinear optical crystal.

[0159] Example 36

[0160] The growth of NaAg3Ga8S by the Bridgman method 14 Infrared nonlinear optical crystal, and the specific operation is carried out according to the following steps:

[0161] The pure NaAg3Ga8S powder obtained in Example 6 14 was loaded into a quartz tube with dimensions of Φ25 mm × 240 mm, evacuated to 10 -3 Pa and then sealed with a hydrogen-oxygen flame. It was placed in a Bridgman furnace and heated to 950 °C at a rate of 17 °C / h. After maintaining the temperature for 80 h until the raw materials were completely melted, the Bridgman furnace was vertically lowered at a speed of 1.2 mm / h. During the lowering process, the growth of NaAg3Ga8S 14 crystal was carried out with a growth period of 27 days. After the crystal growth was completed, the crystal was left in the Bridgman furnace for annealing and cooled to room temperature at a rate of 28 °C / h, thus obtaining a pale yellow NaAg3Ga8S infrared nonlinear optical crystal with dimensions of Φ5 mm × 3.2 mm. 14 Infrared nonlinear optical crystal.

[0162] Example 37

[0163] The crucible descent method grows NaAg3Ga8S 14 Infrared nonlinear optical crystal, the specific operation is carried out according to the following steps:

[0164] The NaAg3Ga8S obtained in Example 7 14 The pure powder sample was placed in a Φ25mm×240mm quartz tube and vacuumed to 10 -3 Pa was then packaged with an oxyhydrogen flame and placed in a crucible descending furnace. The temperature was raised to 930°C at a rate of 19°C / h and kept constant for 65h until the raw materials were completely melted. The crucible descending furnace was then vertically lowered at a rate of 0.2mm / h. During the descent process, NaAg3Ga8S 14 The crystal growth cycle is 32 days. After the crystal growth is completed, the crystal is left in the crucible descending furnace for annealing and cooled to room temperature at a rate of 22℃ / h to obtain a light yellow NaAg3Ga8S with a size of Φ6.2mm×5.0mm. 14 Infrared nonlinear optical crystals.

[0165] Example 38

[0166] The crucible descent method grows NaAg3Ga8S 14 Infrared nonlinear optical crystal, the specific operation is carried out according to the following steps:

[0167] The NaAg3Ga8S obtained in Example 8 14 The pure powder sample was placed in a Φ25mm×240mm quartz tube and vacuumed to 10 -3 Pa was then packaged with an oxyhydrogen flame and placed in a crucible descending furnace. The temperature was raised to 920°C at a rate of 21°C / h and kept constant for 70h until the raw materials were completely melted. The crucible descending furnace was then vertically lowered at a rate of 0.6mm / h. During the descent process, NaAg3Ga8S 14 The crystal growth cycle is 29 days. After the crystal growth is completed, the crystal is left in the crucible descending furnace for annealing and cooled to room temperature at a rate of 27℃ / h to obtain a light yellow NaAg3Ga8S with a size of Φ4.5mm×3.2mm. 14 Infrared nonlinear optical crystals.

[0168] Example 39

[0169] The crucible descent method grows NaAg3Ga8S 14 Infrared nonlinear optical crystal, the specific operation is carried out according to the following steps:

[0170] The NaAg3Ga8S obtained in Example 9 14 The pure powder sample was placed in a Φ25mm×240mm quartz tube and vacuumed to 10 -3After reaching 10 Pa, it is sealed with a hydrogen-oxygen flame and placed in a descending crucible furnace. It is heated to 900 °C at a rate of 23 °C / h and kept at a constant temperature for 80 h until the raw materials are completely melted. Then, the descending crucible furnace is vertically lowered at a speed of 1.0 mm / h. During the descent, NaAg3Ga8S 14 crystal growth is carried out. The growth period is 26 days. After the crystal growth is completed, the crystal is left in the descending crucible furnace for annealing and cooled to room temperature at a rate of 24 °C / h, thus obtaining a pale yellow NaAg3Ga8S with dimensions of Φ5.6 mm × 4.8 mm 14 infrared nonlinear optical crystal.

[0171] Example 40

[0172] The growth of NaAg3Ga8S 14 infrared nonlinear optical crystal by the descending crucible method is specifically operated according to the following steps:

[0173] The NaAg3Ga8S 14 powder pure sample obtained in Example 10 is loaded into a quartz tube with dimensions of Φ25 mm × 240 mm, and the vacuum is pumped to 10 -3 Pa. After sealing with a hydrogen-oxygen flame, it is placed in a descending crucible furnace and heated to 880 °C at a rate of 25 °C / h. It is kept at a constant temperature for 70 h until the raw materials are completely melted. Then, the descending crucible furnace is vertically lowered at a speed of 1.2 mm / h. During the descent, NaAg3Ga8S 14 crystal growth is carried out. The growth period is 23 days. After the crystal growth is completed, the crystal is left in the descending crucible furnace for annealing and cooled to room temperature at a rate of 19 °C / h, thus obtaining a pale yellow NaAg3Ga8S with dimensions of Φ4.4 mm × 3.2 mm 14 infrared nonlinear optical crystal.

[0174] Example 41

[0175] Any one of the NaAg3Ga8S 14 infrared nonlinear optical crystals obtained in Examples 11 - 40 is placed at the position labeled 3 in the Figure 4 device shown. At room temperature, a Q-switched Ho:Tm:Cr:YAG laser is used as the light source, with an incident infrared light wavelength of 2090 nm, and a second harmonic generation light with an output wavelength of 1045 nm is output. The output laser intensity is 0.7 times that of AgGaS2 under the same conditions.

[0176] Example 42

[0177] Any one of the NaAg3Ga8S 14 infrared nonlinear optical crystals obtained in Examples 11 - 40 is placed at the position of 3 according to Figure 4 the figure shown, where 1 is the laser, 2 is the convex lens, and 3 is NaAg3Ga8S14 Infrared nonlinear optical crystal, 4 is a prism, and 5 is a filter; the laser beam emitted from the laser 1 passes through the convex lens 2 and enters the NaAg3Ga8S 14 crystal 3, and the generated outgoing laser beam passes through the prism 4 and the filter 5, thereby obtaining the required laser beam.

[0178] Using the NaAg3Ga8S of the present invention 14 In addition to its use in the preparation of infrared band laser frequency conversion crystals, infrared lasers, infrared communication devices or infrared laser guidance devices, the infrared nonlinear optical crystal can also be used to fabricate frequency doubling generators, up and down frequency converters, optical parametric oscillators, and optical parametric amplifiers.

Claims

1. A compound sodium silver gallium sulfide, characterized in that The molecular formula of the said compound is NaAg3Ga8S 14 , with a molecular weight of 1353.20 g / mol. It has a crystal structure, an asymmetric center, and crystallizes in the Cm space group. It is prepared by the high-temperature solid-phase method.

2. The preparation method of the compound sodium silver thiogallate according to claim 1, characterized in that The high-temperature solid-phase method is adopted, and the specific operation is carried out according to the following steps: a. Mix the Na source material, Ag source material, Ga source material and elemental sulfur evenly according to the molar ratio of Na∶Ag∶Ga∶S = 1∶3∶8∶14, put them into a quartz glass tube with Φ25 mm×240 mm, and use a vacuum pump to evacuate the quartz tube to a vacuum degree of 10 -3 -10 -5 Pa for melting and sealing, where the Na source material is metallic Na, Na2S or NaI; the Ag source material is metallic Ag, Ag2S or AgI; the Ga source material is metallic Ga or Ga2S3; b. Place the sealed quartz tube in a programmable temperature-controlled muffle furnace, heat it to 800 - 950 °C at a rate of 12 - 18 °C / h, carry out solid-phase reaction for 50 - 80 h, then cool it to 650 °C at a rate of 10 - 22 °C / h, turn off the furnace, take out the sample after natural cooling to room temperature, and crush and grind it to obtain a powdery pure sample of sodium silver gallium sulfide.

3. A silver sodium gallium sulfide infrared nonlinear optical crystal, characterized in that, The crystal has a molecular formula of NaAg3Ga8S 14 , a molecular weight of 1353.20 g / mol, has an asymmetric center, and crystallizes in the Cm space group of the monoclinic system. The unit cell parameters are: a = 12.2616(8) Å, b = 11.0956(7) Å, c = 9.2131(6) Å, β = 114.981(2)°, Z = 2, and the volume is 1136.18(13) Å 3 .

4. The preparation method of the silver sodium thio-gallium infrared nonlinear optical crystal according to claim 3, characterized in that Crystal growth is carried out by the high-temperature melt method, chemical vapor transport method or Bridgman method: For growing the infrared nonlinear optical crystal of sodium silver gallium sulfide by the high-temperature melt method, the specific operation is carried out according to the following steps: a. Mix the Na source material, Ag source material, Ga source material and elemental S evenly according to the molar ratio of Na∶Ag∶Ga∶S = 1∶3∶8∶14, put them into a quartz glass tube with Φ25 mm×240 mm, and use a vacuum pump to evacuate the quartz tube to a vacuum degree of 10 -3 -10 -5 Pa for melting and sealing, then put it into a programmable temperature-controlled muffle furnace, heat it at a rate of 12 - 18 °C / h to 800 - 950 °C, carry out solid-phase reaction for 50 - 80 h, then cool it to 650 °C at a rate of 10 - 22 °C / h and turn off the furnace. After natural cooling to room temperature, take out the sample and crush and grind it to obtain a powdery pure sample of sodium silver gallium sulfide. Among them, the Na source material is metallic Na, Na2S or NaI; the Ag source material is metallic Ag, Ag2S or AgI; the Ga source material is metallic Ga or Ga2S3; b. Load the compound powder obtained in step a into a quartz tube, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, heat it at a rate of 10 - 18 °C / h to 900 - 1000 °C, keep it at a constant temperature for 60 - 100 h, slowly cool it to room temperature at a rate of 2 - 8 °C / h, and cut it open after the quartz tube cools to obtain light yellow sodium silver gallium sulfide NaAg3Ga8S 14 infrared nonlinear optical crystal; For growing the infrared nonlinear optical crystal of sodium silver gallium sulfide by the chemical vapor transport method, the specific operation is carried out according to the following steps: a. Mix the Na source material, Ag source material, Ga source material and elemental S evenly according to the molar ratio of Na∶Ag∶Ga∶S = 1∶3∶8∶14, put them into a quartz glass tube with a size of Φ25 mm×240 mm, and use a vacuum pump to evacuate the quartz tube to a vacuum degree of 10 -3 -10 -5 Pa for melting and sealing, then put it into a programmable temperature-controlled muffle furnace, heat it at a rate of 12 - 18 °C / h to 800 - 950 °C, carry out solid-phase reaction for 50 - 80 h, then cool it to 650 °C at a rate of 10 - 22 °C / h and turn off the furnace. After natural cooling to room temperature, take out the sample and crush and grind it to obtain a powdery pure sample of sodium silver gallium sulfide. The Na source material is metallic Na, Na2S or NaI; the Ag source material is metallic Ag, Ag2S or AgI; the Ga source material is metallic Ga or Ga2S3; b. Weigh the compound powder obtained in step a and iodine in a ratio of 1:0.1 - 1, mix them thoroughly, and load them into a quartz tube. Evacuate the tube to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a tube furnace, and perform chemical vapor transport at a high temperature zone of 850 - 950 °C and a low temperature zone of 600 - 750 °C. Grow the sodium silver gallium sulfide crystal through a horizontal or vertical gradient temperature field. Simultaneously heat it to 850 - 950 °C in the high temperature zone and 650 - 750 °C in the low temperature zone at a rate of 13 - 22 °C / h. The growth cycle is 18 - 36 days. After the growth is completed, slowly cool it to room temperature at a rate of 3 - 10 °C / h, turn off the tube furnace, cut it open after the quartz tube cools down, and obtain light yellow sodium silver gallium sulfide NaAg3Ga8S 14 infrared nonlinear optical crystal; For growing the infrared nonlinear optical crystal of sodium silver gallium sulfide by the Bridgman method, the specific operation is carried out according to the following steps: a. Mix the Na source material, Ag source material, Ga source material and elemental S evenly in a molar ratio of Na∶Ag∶Ga∶S = 1∶3∶8∶14, put them into a quartz glass tube with Φ25 mm×240 mm, and use a vacuum pump to evacuate the quartz tube to a vacuum degree of 10 -3 -10 -5 Pa for melting and sealing, then put it into a programmable temperature-controlled muffle furnace, heat it at a rate of 12 - 18 °C / h to 800 - 950 °C, carry out solid-phase reaction for 50 - 80 h, then cool it to 650 °C at a rate of 10 - 22 °C / h and turn off the furnace. After natural cooling to room temperature, take out the sample and crush and grind it to obtain a powdery pure sample of sodium silver gallium sulfide. The Na source material is metallic Na, Na2S or NaI; the Ag source material is metallic Ag, Ag2S or AgI; the Ga source material is metallic Ga or Ga2S3; b. Load the compound powder obtained in step a into a quartz tube with a diameter of Φ25 mm and a length of 240 mm. After evacuating to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a crucible lowering furnace, heat it to 870-980 °C at a rate of 14-28 °C / h, keep it at a constant temperature for 60-80 h until the raw materials are completely melted, and then lower the crucible lowering furnace vertically at a rate of 0.1-2.0 mm / h. During the lowering process, grow the sodium silver gallium sulfide crystal. The growth period is 20-32 days. After the crystal growth is completed, leave the crystal in the crucible lowering furnace for annealing, and cool it to room temperature at a rate of 18-30 °C / h to obtain a pale yellow sodium silver gallium sulfide NaAg3Ga8S 14 infrared nonlinear optical crystal.

5. Use of the infrared nonlinear optical crystal of sodium silver gallium sulfide as claimed in claim 3 in the preparation of an infrared-band laser frequency conversion crystal, an infrared laser, an infrared communication device or an infrared laser guidance device.

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