Compound Selenium Phosphorus Mercury and Selenium Phosphorus Mercury Infrared Nonlinear Optical Crystal, Preparation Method and Application

Abstract

The present invention relates to a compound of mercury selenophosphide, a mercury selenophosphide infrared nonlinear optical crystal, a preparation method and an application thereof. The molecular formula of the compound is Hg7P2Se 12 , and its molecular weight is 1206.79. The molecular formula of the crystal is Hg7P2Se 12 , and its molecular weight is 1206.79. It has no center of symmetry, belongs to the triclinic system, and the space group is P 1. The unit cell parameters are: a = 12.573(2) Å, b = 14.523(2) Å, c = 16.247(2) Å, α = 77.509(5)°, β = 75.191(6)°, γ = 73.051(5)°, Z = 5, and the volume is 2711.1(7) Å 3 . The crystal is prepared by the methods of high-temperature melt method, chemical vapor transport method, flux method or Bridgman method. The crystal has the advantages of high laser damage resistance, moderate nonlinear optical effect, wide transmission band, large hardness, good mechanical properties, not easy to break and deliquesce, easy to process and preserve, etc., and can be used for manufacturing infrared nonlinear optical devices.

Description

Technical Field

[0001] The present invention belongs to the field of preparation of infrared nonlinear optical crystals. Specifically, the present invention relates to the compound mercury selenophosphide (Hg 7 P 2 Se 12 ), and a preparation method and application of a mercury selenophosphide infrared nonlinear optical crystal. Background Art

[0002] Nonlinear optical crystals are a kind of crystal materials with nonlinear optical effects such as frequency doubling, sum frequency, difference frequency, and optical parametric amplification. Only crystals without a center of symmetry can have second-order nonlinear optical effects. By using the second-order nonlinear optical effects of crystals, nonlinear optical devices such as second harmonic generators, up and down frequency converters, and optical parametric oscillators can be made. The laser generated by a laser can be frequency-converted through a nonlinear optical device to obtain more new laser light sources, promoting the development of laser technology in the tunable wavelength range and output power.

[0003] According to the different application bands, nonlinear optical crystal materials can be divided into three categories: ultraviolet nonlinear optical materials, visible and near-infrared nonlinear optical materials, and mid- and far-infrared nonlinear optical materials. Nonlinear optical crystal materials in the ultraviolet, visible, and near-infrared regions can basically meet the requirements of practical applications. For example, in frequency doubling (532 nm) crystals, the mainly used ones are KTP (KTiOPO 4 ), BBO (β-BaB 2 O 4 ), and LBO (LiB 3 O 5 ) crystals; in deep ultraviolet crystals, the practical ones are KBBF (KBe 2 BO 3 F 2 ), ABF (NH 4 B 4 O 6 F), and CBF (CsB 4 O 6 F) for selection. However, the development of mid- and far-infrared nonlinear crystals is relatively slow; currently, most of the commercially available mid- and far-infrared nonlinear optical materials are semiconductor materials with a chalcopyrite structure, such as AgGaQ 2 (Q = S, Se), ZnGeP 2 , etc. However, most of these mid- and far-infrared nonlinear optical materials were developed around the 1970s. Due to some intrinsic performance defects, such as low laser damage threshold and two-photon absorption near 1 μm, the application of these materials in the current high-power laser output field has been greatly limited and can no longer fully meet the requirements of the current development of laser technology. There is an urgent need to develop new mid- and far-infrared nonlinear optical crystal materials with balanced performance. Summary of the Invention

[0004] The object of the present invention is to provide a compound mercury selenide phosphide with the chemical formula Hg 14 P 2 Se 12 .

[0005] Another object of the present invention is to provide a mercury selenide phosphide infrared nonlinear optical crystal of Hg 14 P 2 Se 12 .

[0006] Another object of the present invention is to provide a preparation method of a mercury selenide phosphide nonlinear optical crystal of Hg 14 P 2 Se 12 .

[0007] Another object of the present invention is to provide the use of a mercury selenide phosphide nonlinear optical crystal of Hg 14 P 2 Se 12 .

[0008] A compound mercury selenide phosphide according to the present invention has a molecular formula of Hg 7 P 2 Se 12 , a molecular weight of 2413.59, a crystal structure, belonging to the triclinic system, space group P1, and is prepared by the high-temperature melt method.

[0009] The preparation method of the compound mercury selenide phosphide is carried out according to the following steps:

[0010] a. According to the molar ratio of Hg∶P∶Se = 7∶2∶12, the Hg source material is Hg, Hg 2 Cl 2 , HgI 2 or HgSe; the P source material is P or P 2 Se 5 , and the selenium source material is Se are mixed evenly to obtain a mixture;

[0011] b. Grind the mixture obtained in step a to 100 mesh, load it into a quartz container, and evacuate it to 10 - 3 Pa for melting and sealing;

[0012] c. Place the sealed sample in step b in a muffle furnace, heat it to 450 - 550 °C at a rate of 10 - 40 °C / h, keep it at a constant temperature for 40 - 60 h, then cool it to 300 °C at a rate of 10 - 20 °C / h, take out the sample after cooling, and crush and grind it to obtain a powdery pure sample of mercury selenide phosphide.

[0013] A mercury selenide phosphorus infrared nonlinear optical crystal, the crystal formula of which is Hg 7 P 2 Se 12 , with a molecular weight of 2413.59, having no center of symmetry, belonging to the triclinic system, the space group is P1, and the unit cell parameters are α = 77.509(5)°, β = 75.191(6)°, γ = 73.051(5)°, Z = 5.

[0014] The preparation method of the mercury selenide phosphorus infrared nonlinear optical crystal adopts the high-temperature melt method, chemical vapor transport method, flux method or Bridgman method for crystal growth:

[0015] When growing the mercury selenide phosphorus infrared nonlinear optical crystal by the high-temperature melt method, the specific operation is carried out according to the following steps:

[0016] a. After mixing the Hg source material, P source material and elemental Se evenly according to the molar ratio of Hg∶P∶Se = 7∶2∶12, grinding to 100 mesh, loading into a quartz tube, evacuating to 10 -3 Pa and sealing it, putting it into a muffle furnace, heating it to 450 - 550 °C at a rate of 10 - 40 °C / h, keeping it at a constant temperature for 60 - 100 h, cooling it to 300 °C at a rate of 10 - 20 °C / h, taking out the sample after cooling, and crushing and grinding it to obtain powdery Hg 7 P 2 Se 12 compound, where the Hg source material is Hg, Hg 2 Cl 2 , HgI 2 or HgSe; the P source material is P or P 2 Se 5 , and the selenium source material is Se;

[0017] b. Loading the compound powder into a quartz tube, evacuating to 10 -3 Pa, sealing it with a hydrogen-oxygen flame, placing it in a muffle furnace, slowly heating it to 450 - 500 °C, keeping it at a constant temperature for 24 - 72 h, then slowly cooling it to room temperature at a rate of 1 - 5 °C / h, turning off the muffle furnace, and cutting it open after the quartz tube cools to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal;

[0018] When growing the mercury selenide phosphorus infrared nonlinear optical crystal by the chemical vapor transport method, the specific operation is carried out according to the following steps:

[0019] a. Directly mixing the Hg source material, P source material and elemental Se evenly according to the molar ratio of Hg∶P∶Se = 7∶2∶12, loading into a quartz tube, evacuating to 10-3 Pa, encapsulated with a hydrogen-oxygen flame and placed in a tubular growth furnace, where the Hg source material is Hg, Hg 2 Cl 2 , HgI 2 or HgSe; the P source material is P or P 2 Se 5 , and the selenium source material is Se;

[0020] b. Perform chemical vapor transport in the tubular growth furnace, and grow the crystal of Hg 7 P 2 Se 12 by a horizontal or vertical gradient temperature field. Heat it to 450 - 550 °C at a rate of 25 °C / h, with a growth period of 8 - 20 days. After the growth is completed, slowly cool it to room temperature at a rate of 1 - 5 °C / h, turn off the tubular growth furnace, and cut it after the quartz tube cools. Obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal at the low-temperature end;

[0021] The method for growing a mercury selenide phosphide infrared nonlinear optical crystal by the flux method is specifically operated according to the following steps:

[0022] a. Mix the Hg source material, P source material, and Se source material evenly according to a molar ratio of 6.5 - 8:2:12 - 14, put them into a clean graphite crucible, place the graphite crucible into a quartz tube, and use a vacuum pump to evacuate the quartz tube to 10 -3 Pa, then perform melting and sealing, and place the quartz tube into a programmable temperature-controlled muffle furnace. Heat it to 450 - 550 °C at a rate of 10 - 40 °C / h, keep it at a constant temperature for 60 - 100 h, cool it to 300 °C at a rate of 10 - 20 °C / h, take out the sample after cooling, and crush and grind it to obtain Hg 7 P 2 Se 12 powder, where the Hg source material is Hg, Hg 2 Cl 2 , HgI 2 or HgSe; the P source material is P or P 2 Se 5 , and the selenium source material is Se;

[0023] b. Mix the mercury selenide phosphide powder obtained in step a with a flux of Se, HgSe, or Hg 2 Cl 2 at a mass ratio of 1:0.5 - 4.5, and load it into a quartz tube with a diameter of 35 mm and a length of 20 cm. Use a vacuum pump to evacuate the quartz tube to 10 -3Pa, perform melting seal. Put the sealed quartz tube into a programmable temperature-controlled muffle furnace and heat it to 430 - 480 °C. After maintaining a constant temperature for 30 - 68 h, cool it to room temperature at a cooling rate of 2 - 9 °C / h to obtain black Hg 7 P 2 Se 12 Infrared nonlinear optical crystal;

[0024] The method for growing mercury cadmium telluride infrared nonlinear optical crystal by the Bridgman method is carried out according to the following steps:

[0025] a. Mix the Hg source material, P source material and Se source material evenly according to a molar ratio of 6.5 - 8:2:12 - 14, put them into a clean graphite crucible, place the graphite crucible into a quartz tube, and use a vacuum pump to evacuate the quartz tube to 10 -3 Pa. Then perform melting seal, put the quartz tube into a programmable temperature-controlled muffle furnace, and heat it to 450 - 550 °C at a rate of 10 - 40 °C / h. Keep the temperature constant for 60 - 100 h, then cool it to 300 °C at a rate of 10 - 20 °C / h. After cooling, take out the sample, crush and grind it to obtain powdered Hg 7 P 2 Se 12 , then load it into the quartz tube again, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a Bridgman furnace, and heat it to 480 - 560 °C at a rate of 5 - 20 °C / h. Keep the temperature constant for 60 - 100 h until the raw materials melt;

[0026] Or mix the Hg source material, P source material and Se source material evenly according to a molar ratio of 6.5 - 8:2:12 - 14, put them into a clean graphite crucible, place the graphite crucible into a quartz tube, and use a vacuum pump to evacuate the quartz tube to 10 -3 Pa. Then perform melting seal, put the quartz tube into a programmable temperature-controlled Bridgman furnace, and heat it to 450 - 550 °C at a rate of 10 - 40 °C / h until the raw materials melt. The Hg source material is Hg, Hg 2 Cl 2 , HgI 2 Or HgSe; the P source material is P or P 2 Se 5 , and the Se source material is Se;

[0027] b. After the raw materials are completely melted, lower the Bridgman furnace vertically at a speed of 0.1 - 3 mm / h. During the lowering process, perform Hg 7 P 2 Se 12Crystal growth with a growth period of 20 - 40 days. After the crystal growth is completed, the crystal is left in the crucible drop furnace for annealing and cooled to room temperature at a rate of 40 - 60 °C / h to obtain black Hg 7 P 2 Se 12 Infrared nonlinear optical crystal.

[0028] Use of the mercury selenide phosphorus infrared nonlinear optical crystal in the preparation of infrared band laser frequency conversion crystals, infrared lasers, infrared electro - optical devices, infrared communication devices or infrared laser guidance devices.

[0029] A compound mercury selenide phosphorus Hg of the present invention 14 P 2 Se 12 Is prepared according to the following chemical reaction formula:

[0030] (1) 7Hg + 2P + 12Se = Hg 7 P 2 Se 12 ;

[0031] (2) 7Hg + P 2 Se 5 + 7Se = Hg 7 P 2 Se 12 ;

[0032] (3) 7HgSe + P 2 Se 5 = Hg 7 P 2 Se 12 ;

[0033] (4) 7HgSe + 2P + 5Se = Hg 7 P 2 Se 12 ;

[0034] (5) 21Hg 2 Cl 2 + 12P + 72Se = 6Hg 7 P 2 Se 12 + 14PCl 3

[0035] (6) 21HgI + 6P + 36Se = 3Hg 7 P 2 Se 12 + 7PI 3 。

[0036] The preparation methods of the mercury selenide phosphorus infrared nonlinear optical crystal of the present invention can all obtain Hg with a size of centimeter - level7 P 2 Se 12 Nonlinear optical crystal; by using a large-sized crucible and extending the growth period, relatively larger-sized Hg can be obtained. 7 P 2 Se 12 Nonlinear optical crystal.

[0037] According to the crystallographic data of the crystal, the crystal blank is oriented, the crystal is cut at the required angles, thicknesses, and cross-sectional dimensions, and the light-passing surface of the crystal is polished, and then it can be used as a nonlinear optical device.

[0038] The application of the mercury selenide phosphorus infrared nonlinear optical crystal described in the present invention in the field of laser technology includes uses in preparing infrared-band laser frequency conversion crystals, infrared lasers, infrared electro-optic devices, infrared communication devices, or infrared laser guidance devices.

[0039] The mercury selenide phosphorus infrared nonlinear optical crystal described in the present invention has the advantages of relatively low synthesis temperature, being transparent and inclusion-free, low cost, and being easy to obtain relatively large-sized crystals; the obtained Hg 7 P 2 Se 12 The infrared nonlinear optical crystal and device have the advantages of anti-laser damage, moderate nonlinear optical effect, wide light-transmitting band, relatively large hardness, good mechanical properties, not being easily fragmented and deliquescent, being easy to process and preserve, etc.; the Hg 7 P 2 Se 12 Nonlinear optical crystal can be used to fabricate infrared nonlinear optical devices. Description of the Drawings

[0040] Figure 1 It is a schematic structural diagram of the mercury selenide phosphorus crystal of the present invention;

[0041] Figure 2 It is a comparison diagram of the X-ray diffraction pattern of the polycrystalline powder of the mercury selenide phosphorus crystal of the present invention before and after melting with the theoretical value;

[0042] Figure 3 It is a working principle diagram of the optical device of the present invention, where 1 is a laser, 2 is a convex lens, 3 is the Hg 7 P 2 Se 12 Nonlinear optical crystal after post-treatment and optical processing, 4 is a prism, and 5 is a filter. Detailed Embodiments

[0043] Any feature disclosed in this specification, unless specifically recited, may be replaced by other equivalent or similar-purpose alternative features. Unless specifically recited, each feature is only an example of a series of equivalent or similar features. This is only for helping to understand the present invention and should not be regarded as a specific limitation to the present invention.

[0044] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0045] Example 1

[0046] According to the reaction formula 7Hg + 2P + 12Se = Hg 7 P 2 Se 12 To prepare the compound Hg 7 P 2 Se 12 :

[0047] After mixing 1.404 g of Hg, 0.062 g of P and 0.948 g of Se evenly, grind them to 100 mesh, load them into a quartz tube, evacuate to 10 -3 Pa and perform melting and encapsulation, put it into a muffle furnace, heat it to 500 °C at a rate of 25 °C / h, keep it at a constant temperature for 48 h, cool it to 200 °C at a rate of 10 °C / h and then turn off the muffle furnace. After cooling, take out the sample, and crush and grind it to obtain powdery Hg 7 P 2 Se 12 compound.

[0048] Example 2

[0049] According to the reaction formula 7Hg + P 2 Se 5 + 7Se = Hg 7 P 2 Se 12 To prepare the compound Hg 7 P 2 Se 12 :

[0050] After mixing 1.404 g of Hg, 0.455 g of P 2 Se 5 and 0.553 g of Se evenly, grind them to 100 mesh, load them into a quartz tube, evacuate to 10 -3 Pa and perform melting and encapsulation, put it into a muffle furnace, heat it to 480 °C at a rate of 25 °C / h, keep it at a constant temperature for 48 h, cool it to 200 °C at a rate of 10 °C / h and then turn off the muffle furnace. After cooling, take out the sample, and crush and grind it to obtain powdery Hg 7 P 2 Se 12 compound.

[0051] Example 3

[0052] According to the reaction formula 7HgSe + P 2 Se 5 = Hg 7 P 2 Se 12 To prepare the compound Hg 7 P 2 Se 12 :

[0053] Mix 3.206 grams of HgSe and 0.455 grams of P 2 Se 5 After mixing evenly, grind to 100 mesh, load into a quartz tube, evacuate to 10 -3 Pa and perform melting and encapsulation. Place it in a muffle furnace, heat it to 520 °C at a rate of 15 °C / h, keep it at a constant temperature for 60 h, cool it to 200 °C at a rate of 15 °C / h, then turn off the muffle furnace. After cooling, take out the sample, and crush and grind it to obtain powdery Hg 7 P 2 Se 12 compound.

[0054] Example 4

[0055] According to the reaction formula 7HgSe + 2P + 5Se = Hg 7 P 2 Se 12 To prepare the compound Hg 7 P 2 Se 12 :

[0056] Mix 1.404 grams of HgSe, 0.062 grams of P, and 0.395 grams of Se evenly, grind to 100 mesh, load into a quartz tube, evacuate to 10 -3 Pa and perform melting and encapsulation. Place it in a muffle furnace, heat it to 550 °C at a rate of 25 °C / h, keep it at a constant temperature for 48 h, cool it to 200 °C at a rate of 10 °C / h, then turn off the muffle furnace. After cooling, take out the sample, and crush and grind it to obtain powdery Hg 7 P 2 Se 12 compound.

[0057] Example 5

[0058] According to the reaction formula 21Hg 2 Cl 2 + 12P + 72Se = 6Hg 7 P 2 Se 12 + 14PCl 3 To prepare the compound Hg 7 P2 Se 12 :

[0059] Mix 9.889 g of Hg 2 Cl 2 , 0.372 g of P and 5.692 g of Se evenly, grind to 100 mesh, load into a quartz tube, evacuate to 10 -3 Pa and perform melting and encapsulation, place in a muffle furnace, heat up to 450 °C at a rate of 40 °C / h, keep the temperature constant for 48 h, cool down to 200 °C at a rate of 10 °C / h and then turn off the muffle furnace. After cooling, take out the sample and crush and grind to obtain powdered Hg 7 P 2 Se 12 compound.

[0060] Example 6

[0061] According to the reaction formula 21HgI + 6P + 36Se = 3Hg 7 P 2 Se 12 + 7PI 3 Prepare the compound Hg 7 P 2 Se 12 :

[0062] Mix 9.548 g of HgI, 0.186 g of P, and 2.846 g of Se evenly, grind to 100 mesh, load into a quartz tube, evacuate to 10 -3 Pa and perform melting and encapsulation, place in a muffle furnace, heat up to 500 °C at a rate of 20 °C / h, keep the temperature constant for 36 h, cool down to 200 °C at a rate of 10 °C / h and then turn off the muffle furnace. After cooling, take out the sample and crush and grind to obtain powdered Hg 7 P 2 Se 12 compound.

[0063] Example 7

[0064] For the growth of mercury selenide phosphide infrared nonlinear optical crystal by the high-temperature melt method, the specific operation is carried out according to the following steps:

[0065] Load the powder obtained in Example 1 into a quartz tube with Φ25 mm × 240 mm, evacuate to 10 -3 Pa, seal with a hydrogen-oxygen flame, place in a muffle furnace, slowly heat up to 520 °C, keep the temperature constant for 60 h, then slowly cool down to room temperature at a rate of 1 °C / h, turn off the muffle furnace. After the quartz tube cools, cut it open to obtain a Φ3 × 2 mm black Hg 14 P 2 Se 12 infrared nonlinear optical crystal.

[0066] Example 8

[0067] The growth of mercury selenide phosphide infrared nonlinear optical crystal by the high-temperature melt method is specifically operated according to the following steps:

[0068] Put the compound powder obtained in Example 2 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, slowly raise the temperature to 500°C, keep it at a constant temperature for 55h; slowly cool it to 200°C at a rate of 3°C / h, turn off the muffle furnace, cut it after the quartz tube cools, and obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0069] Example 9

[0070] The growth of mercury selenide phosphide infrared nonlinear optical crystal by the high-temperature melt method is specifically operated according to the following steps:

[0071] Put the compound obtained in Example 3 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, slowly raise the temperature to 480°C, keep it at a constant temperature for 36h; slowly cool it to 200°C at a rate of 2.5°C / h, turn off the muffle furnace, cut it after the quartz tube cools, and obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0072] Example 10

[0073] The growth of mercury selenide phosphide infrared nonlinear optical crystal by the high-temperature melt method is specifically operated according to the following steps:

[0074] Put the compound obtained in Example 4 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, slowly raise the temperature to 520°C, keep it at a constant temperature for 40h; slowly cool it to 200°C at a rate of 5°C / h, turn off the muffle furnace, cut it after the quartz tube cools, and obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0075] Example 11

[0076] The growth of mercury selenide phosphide infrared nonlinear optical crystal by the high-temperature melt method is specifically operated according to the following steps:

[0077] The compound obtained in Example 5 was loaded into a quartz glass tube with a diameter of Φ25mm×240mm, evacuated to 10 -3 Pa, sealed with a hydrogen-oxygen flame, placed in a muffle furnace, slowly heated to a temperature of 450 °C, and kept at a constant temperature for 70 h; slowly cooled to 200 °C at a rate of 3.5 °C / h, the muffle furnace was turned off, and after the quartz tube cooled, it was cut open to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0078] Example 12

[0079] For the growth of mercury selenide phosphide infrared nonlinear optical crystal by the high-temperature melt method, the specific operation is carried out according to the following steps:

[0080] The compound obtained in Example 6 was loaded into a quartz glass tube with a diameter of Φ25mm×240mm, evacuated to 10 -3 Pa, sealed with a hydrogen-oxygen flame, placed in a muffle furnace, slowly heated to a temperature of 500 °C, and kept at a constant temperature for 24 h; slowly cooled to 200 °C at a rate of 4.5 °C / h, the muffle furnace was turned off, and after the quartz tube cooled, it was cut open to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0081] Example 13

[0082] For the growth of mercury selenide phosphide infrared nonlinear optical crystal by the high-temperature melt method, the specific operation is carried out according to the following steps:

[0083] a. According to the reaction formula 7Hg + 2P + 12Se = Hg 7 P 2 Se 12 , directly mix 1.404 g of Hg, 0.062 g of P and 0.948 g of Se (i.e., Hg:P:Se = 0.007 mol:0.002 mol:0.012 mol) evenly, grind to 100 mesh, load into a quartz glass tube with a diameter of Φ25mm×240mm, evacuate to 10 -3 Pa, seal with a hydrogen-oxygen flame, place in a muffle furnace, and slowly heat to a temperature of 520 °C and keep at a constant temperature for 60 h;

[0084] b. Slowly cool to 200 °C at a rate of 2.5 °C / h, turn off the muffle furnace, and after the quartz tube cools, cut it open to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0085] Example 14

[0086] The growth of mercury phosphide selenide infrared nonlinear optical crystal by the high-temperature melt method is carried out according to the following steps:

[0087] a. According to the reaction formula 7Hg + P 2 Se 5 + 7Se = Hg 7 P 2 Se 12 , directly take 1.404 g of Hg, 0.455 g of P 2 Se 5 and 0.553 g of Se (i.e., Hg:P 2 Se 5 :Se = 0.007 mol:0.001 mol:0.007 mol), after mixing evenly, grind to 100 mesh, load into a quartz glass tube with Φ25mm×240mm, evacuate to 10 -3 Pa, seal with a hydrogen-oxygen flame, place in a muffle furnace, slowly raise the temperature to 500 °C, and keep the temperature constant for 60 h;

[0088] b. Slowly cool to 200 °C at a rate of 3 °C / h, turn off the muffle furnace, cut it after the quartz tube cools, and obtain a Φ3×3mm black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0089] Example 15

[0090] The growth of mercury phosphide selenide infrared nonlinear optical crystal by the high-temperature melt method is carried out according to the following steps:

[0091] a. According to the reaction formula 7HgSe + P 2 Se 5 = Hg 7 P 2 Se 12 , directly take 3.206 g of HgSe and 0.455 g of P 2 Se 5 (i.e., HgSe:P 2 Se 5 = 0.007 mol:0.001 mol), after mixing evenly, grind to 100 mesh, load into a quartz glass tube with Φ25mm×240mm, evacuate to 10 -3 Pa, seal with a hydrogen-oxygen flame, place in a muffle furnace, slowly raise the temperature to 480 °C, and keep the temperature constant for 60 h;

[0092] b. Slowly cool to 200 °C at a rate of 2.5 °C / h, turn off the muffle furnace, cut it after the quartz tube cools, and obtain a Φ2×2mm black Hg 7 P2 Se 12 Infrared nonlinear optical crystal

[0093] Example 16

[0094] The growth of mercury selenide phosphide infrared nonlinear optical crystal by the high-temperature melt method is specifically carried out according to the following steps:

[0095] a. According to the reaction formula 7HgSe + 2P + 5Se = Hg 7 P 2 Se 12 , directly mix 1.404 g of HgSe, 0.062 g of P, and 0.395 g of Se (i.e., HgSe:P:Se = 0.007 mol:0.002 mol:0.005 mol), grind to 100 mesh, load into a quartz glass tube with Φ25mm×240mm, evacuate to 10 -3 Pa, seal with a hydrogen-oxygen flame, place in a muffle furnace, slowly raise the temperature to 520 °C, and keep it at a constant temperature for 60 h;

[0096] b. Slowly cool to 200 °C at a rate of 2.5 °C / h, turn off the muffle furnace, cut the quartz tube after cooling, and obtain a black Hg 7 P 2 Se 12 Infrared nonlinear optical crystal

[0097] Example 17

[0098] The growth of mercury selenide phosphide infrared nonlinear optical crystal by the high-temperature melt method is specifically carried out according to the following steps:

[0099] a. According to the reaction formula 21Hg 2 Cl 2 + 12P + 72Se = 6Hg 7 P 2 Se 12 + 14PCl 3 , directly mix 9.889 g of Hg 2 Cl 2 , 0.372 g of P, and 5.692 g of Se (i.e., Hg 2 Cl 2 :P:Se = 0.021 mol:0.012 mol:0.072 mol), grind to 100 mesh after uniform mixing, load into a quartz glass tube with Φ25mm×240mm, evacuate to 10 -3 Pa, seal with a hydrogen-oxygen flame, place in a muffle furnace, slowly raise the temperature to 480 °C, and keep it at a constant temperature for 60 h;

[0100] b. Slowly cool it to 200 °C at a rate of 3.5 °C / h, turn off the muffle furnace, and cut it after the quartz tube has cooled to obtain black Hg with a diameter of Φ5×3 mm. 7 P 2 Se 12 Infrared nonlinear optical crystal.

[0101] Example 18

[0102] For the growth of mercury selenide phosphide infrared nonlinear optical crystal by the high-temperature melt method, the specific operation is carried out according to the following steps:

[0103] a. According to the reaction formula 21HgI + 6P + 36Se = 3Hg 7 P 2 Se 12 + 7PI 3 , directly mix 9.548 grams of HgI, 0.186 grams of P, and 2.846 grams of Se (i.e., HgI:P:Se = 0.021 mol:0.006 mol:0.036 mol), grind it to 100 mesh after uniform mixing, load it into a quartz glass tube with a diameter of Φ25 mm × 240 mm, evacuate it to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, slowly raise the temperature to 500 °C, and keep it at a constant temperature for 60 h;

[0104] b. Slowly cool it to 200 °C at a rate of 3.5 °C / h, turn off the muffle furnace, and cut it after the quartz tube has cooled to obtain black Hg with a diameter of Φ6×2 mm. 7 P 2 Se 12 Infrared nonlinear optical crystal.

[0105] Example 19

[0106] For the growth of mercury selenide phosphide infrared nonlinear optical crystal by the chemical vapor transport method, the specific operation is carried out according to the following steps:

[0107] Perform chemical vapor transport on the compound obtained in Example 1 in a tube-type growth furnace, and grow Hg 7 P 2 Se 12 crystal by a horizontal gradient temperature field. Raise the temperature to 550 °C at a rate of 25 °C / h, with a growth period of 10 days. After the growth is completed, slowly cool it to 200 °C at a rate of 1 °C / h, turn off the tube-type growth furnace, and cut it after the quartz tube has cooled to obtain black Hg with a diameter of Φ2×1 mm. 7 P 2 Se 12 Infrared nonlinear optical crystal.

[0108] Example 20

[0109] The growth of mercury cadmium telluride infrared nonlinear optical crystal by chemical vapor transport method is carried out according to the following steps:

[0110] The compound obtained in Example 2 is subjected to chemical vapor transport in a tubular growth furnace, and crystal growth of Hg 7 P 2 Se 12 is carried out through a vertical gradient temperature field. It is heated to 450 °C at a rate of 25 °C / h, the growth period is 8 days, and after the growth is completed, it is slowly cooled to room temperature at a rate of 2 °C / h. The tubular growth furnace is turned off, and after the quartz tube is cooled, it is cut open to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal with a size of Φ2×2 mm.

[0111] Example 21

[0112] The growth of mercury cadmium telluride infrared nonlinear optical crystal by chemical vapor transport method is carried out according to the following steps:

[0113] The compound obtained in Example 3 is subjected to chemical vapor transport in a tubular growth furnace, and crystal growth of Hg 7 P 2 Se 12 is carried out through a horizontal gradient temperature field. It is heated to 520 °C at a rate of 25 °C / h, the growth period is 10 days, and after the growth is completed, it is slowly cooled to room temperature at a rate of 3 °C / h. The tubular growth furnace is turned off, and after the quartz tube is cooled, it is cut open to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal with a size of Φ2.5×1.5 mm.

[0114] Example 22

[0115] The growth of mercury cadmium telluride infrared nonlinear optical crystal by chemical vapor transport method is carried out according to the following steps:

[0116] The compound obtained in Example 4 is subjected to chemical vapor transport in a tubular growth furnace, and crystal growth of Hg 7 P 2 Se 12 is carried out through a horizontal gradient temperature field. It is heated to 530 °C at a rate of 25 °C / h, the growth period is 15 days, and after the growth is completed, it is slowly cooled to room temperature at a rate of 4 °C / h. The tubular growth furnace is turned off, and after the quartz tube is cooled, it is cut open to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal with a size of Φ3×1 mm.

[0117] Example 23

[0118] The growth of mercury phosphoselenide infrared nonlinear optical crystal by chemical vapor transport method is carried out according to the following specific steps:

[0119] Carry out chemical vapor transport on the compound obtained in Example 5 in a tubular growth furnace, and carry out Hg 7 P 2 Se 12 crystal growth through a horizontal gradient temperature field. Raise the temperature to 500 °C at a rate of 25 °C / h, with a growth period of 18 days. After the growth is completed, slowly cool it to room temperature at a rate of 5 °C / h, turn off the tubular growth furnace, and cut it open after the quartz tube cools to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal with a size of Φ8×5 mm.

[0120] Example 24

[0121] The growth of mercury phosphoselenide infrared nonlinear optical crystal by chemical vapor transport method is carried out according to the following specific steps:

[0122] Carry out chemical vapor transport on the compound obtained in Example 6 in a tubular growth furnace, and carry out Hg 7 P 2 Se 12 crystal growth through a horizontal gradient temperature field. Raise the temperature to 490 °C at a rate of 25 °C / h, with a growth period of 20 days. After the growth is completed, slowly cool it to room temperature at a rate of 3.5 °C / h, turn off the muffle furnace, and cut it open after the quartz tube cools to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal with a size of Φ4×4 mm.

[0123] Example 25

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

[0125] a. According to the reaction formula 7Hg + 2P + 12Se = Hg 7 P 2 Se 12 , directly mix 1.404 g of Hg, 0.062 g of P and 0.948 g of Se (i.e., Hg:P:Se = 0.007 mol:0.002 mol:0.012 mol) evenly, then load them into a quartz glass tube with a size of Φ25 mm×240 mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, and place it in a tubular growth furnace;

[0126] b. Heat to 550 °C at a rate of 25 °C / h and perform chemical vapor transport in a tube furnace. Hg 7 P 2 Se 12 crystal growth is carried out through a horizontal gradient temperature field. The growth period is 10 days. After the growth is completed, slowly cool to 200 °C at a rate of 1 °C / h, turn off the tube furnace, and cut it after the quartz tube cools to obtain a Φ2×1 mm black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0127] Example 26

[0128] For the growth of mercury selenide phosphide infrared nonlinear optical crystal by the chemical vapor transport method, the specific operation is carried out according to the following steps:

[0129] a. According to the reaction formula 7Hg + P 2 Se 5 + 7Se = Hg 7 P 2 Se 12 , directly weigh 1.404 g of Hg, 0.455 g of P 2 Se 5 and 0.553 g of Se (i.e., Hg:P 2 Se 5 :Se = 0.007 mol:0.001 mol:0.007 mol), mix them evenly, load them into a quartz glass tube with a diameter of Φ25 mm × 240 mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, and place it in a tube furnace;

[0130] b. Heat to 530 °C at a rate of 25 °C / h and perform chemical vapor transport in a tube furnace. Hg 7 P 2 Se 12 crystal growth is carried out through a horizontal gradient temperature field. The growth period is 10 days. After the growth is completed, slowly cool to 600 °C at a rate of 1 °C / h, turn off the tube furnace, and cut it after the quartz tube cools to obtain a Φ2×2 mm black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0131] Example 27

[0132] For the growth of mercury selenide phosphide infrared nonlinear optical crystal by the chemical vapor transport method, the specific operation is carried out according to the following steps:

[0133] a. According to the reaction formula 7HgSe + P 2 Se 5= Hg 7 P 2 Se 12 , directly mix 3.206 g of HgSe and 0.455 g of P 2 Se 5 (i.e., HgSe:P 2 Se 5 = 0.007 mol:0.001 mol), after uniform mixing, load it into a quartz glass tube with Φ25 mm × 240 mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, and place it in a tube furnace;

[0134] b. Heat it to 520 °C at a rate of 25 °C / h, perform chemical vapor transport in the tube furnace, and grow Hg 7 P 2 Se 12 crystals through a horizontal gradient temperature field. The growth period is 10 days. After the growth is completed, slowly cool it to 200 °C at a rate of 1 °C / h, turn off the tube furnace, and cut it after the quartz tube cools to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0135] Example 28

[0136] For growing the mercury selenide phosphorus infrared nonlinear optical crystal by the chemical vapor transport method, the specific operation is carried out according to the following steps:

[0137] a. According to the reaction formula 7HgSe + 2P + 5Se = Hg 7 P 2 Se 12 , directly mix 1.404 g of HgSe, 0.062 g of P, and 0.395 g of Se (i.e., HgSe:P:Se = 0.007 mol:0.002 mol:0.005 mol), after uniform mixing, load it into a quartz glass tube with Φ25 mm × 240 mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, and place it in a tube furnace;

[0138] b. Heat it to 530 °C at a rate of 25 °C / h, perform chemical vapor transport in the tube furnace, and grow Hg 7 P 2 Se 12 crystals through a horizontal gradient temperature field. The growth period is 10 days. After the growth is completed, slowly cool it to 200 °C at a rate of 1 °C / h, turn off the tube furnace, and cut it after the quartz tube cools to obtain a black Hg 7 P 2 Se12 Infrared nonlinear optical crystal.

[0139] Example 29

[0140] For the growth of mercury selenide phosphide infrared nonlinear optical crystal by chemical vapor transport method, the specific operation is carried out according to the following steps:

[0141] a. According to the reaction formula 21Hg 2 Cl 2 +12P + 72Se = 6Hg 7 P 2 Se 12 +14PCl 3 , directly mix 9.889 grams of Hg 2 Cl 2 , 0.372 grams of P, and 5.692 grams of Se (i.e., Hg 2 Cl 2 :P:Se = 0.021mol:0.012mol:0.072mol), after uniform mixing, load it into a quartz glass tube with Φ25mm×240mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, and place it in a tube furnace;

[0142] b. Raise the temperature to 500 °C at a rate of 25 °C / h, carry out chemical vapor transport in the tube furnace, and grow Hg 7 P 2 Se 12 crystal through a horizontal gradient temperature field. The growth cycle is 10 days. After the growth is completed, slowly cool it to 200 °C at a rate of 1 °C / h, turn off the tube furnace, and cut it after the quartz tube cools to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0143] Example 30

[0144] For the growth of mercury selenide phosphide infrared nonlinear optical crystal by chemical vapor transport method, the specific operation is carried out according to the following steps:

[0145] a. According to the reaction formula 21HgI + 6P + 36Se = 3Hg 7 P 2 Se 12 +7PI 3 , directly mix 9.548 grams of HgI, 0.186 grams of P, and 2.846 grams of Se (i.e., HgI:P:Se = 0.021mol:0.006mol:0.036mol), after uniform mixing, load it into a quartz glass tube with Φ25mm×240mm, evacuate to 10 -3Pa, encapsulate it with a hydrogen-oxygen flame, place it in a muffle furnace,;

[0146] b. Slowly raise the temperature to 490 °C, conduct chemical vapor transport in a tube furnace, and perform Hg 7 P 2 Se 12 crystal growth through a horizontal gradient temperature field. The growth cycle is 15 days. After the growth is completed, slowly cool it to 200 °C at a rate of 3.5 °C / h, turn off the muffle furnace, and cut it after the quartz tube cools to obtain a Φ4×4 mm black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0147] Example 31

[0148] For the growth of mercury cadmium telluride infrared nonlinear optical crystal by the Bridgman method, the specific operation is carried out according to the following steps:

[0149] a. After grinding 5 g of the pure-phase mercury cadmium telluride powder obtained in Example 1 evenly, put it into a crucible, place it in a quartz glass tube with a diameter of Φ25 mm×240 mm, and evacuate it to 10 -3 Pa, encapsulate it with a hydrogen-oxygen flame, place it in a Bridgman furnace, and slowly raise the temperature to 530 °C to melt the raw materials;

[0150] b. After the raw materials are completely melted, lower the Bridgman furnace vertically at a speed of 1 mm / h. During the lowering process, mercury cadmium telluride crystal growth is carried out. The growth cycle is 15 days. After the crystal growth is completed, anneal the crystal in the Bridgman furnace and cool it to room temperature at a rate of 43 °C / h to obtain a Φ3.9×3.3 mm black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0151] Example 32

[0152] For the growth of mercury cadmium telluride infrared nonlinear optical crystal by the Bridgman method, the specific operation is carried out according to the following steps:

[0153] a. After grinding 5 g of the pure-phase mercury cadmium telluride powder obtained in Example 2 evenly, put it into a crucible, place it in a quartz glass tube with a diameter of Φ25 mm×240 mm, and evacuate it to 10 -3 Pa, encapsulate it with a hydrogen-oxygen flame, place it in a Bridgman furnace, and slowly raise the temperature to 518 °C to melt the raw materials;

[0154] b. After the raw materials are completely melted, lower the crucible furnace vertically at a speed of 1 mm / h. During the descent, grow the mercury selenide phosphide crystal. The growth period is 15 days. After the crystal growth is completed, leave the crystal in the crucible descent furnace for annealing, and cool it to room temperature at a rate of 46 °C / h to obtain a black Hg with a size of Φ3.3×2.5 mm. 7 P 2 Se 12 Infrared nonlinear optical crystal.

[0155] Example 33

[0156] The method for growing mercury selenide phosphide infrared nonlinear optical crystal by the Bridgman method is specifically operated according to the following steps:

[0157] a. After grinding 5 g of the pure-phase mercury selenide phosphide powder obtained in Example 3 evenly, put it into a crucible, place it in a quartz glass tube with a size of Φ25 mm×240 mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in the crucible descent furnace, and slowly raise the temperature to 525 °C to melt the raw materials;

[0158] b. After the raw materials are completely melted, lower the crucible furnace vertically at a speed of 1 mm / h. During the descent, grow the mercury selenide phosphide crystal. The growth period is 15 days. After the crystal growth is completed, leave the crystal in the crucible descent furnace for annealing, and cool it to room temperature at a rate of 50 °C / h to obtain a black Hg with a size of Φ4.1×2.1 mm. 7 P 2 Se 12 Infrared nonlinear optical crystal.

[0159] Example 34

[0160] The method for growing mercury selenide phosphide infrared nonlinear optical crystal by the Bridgman method is specifically operated according to the following steps:

[0161] a. After grinding 5 g of the pure-phase mercury selenide phosphide powder obtained in Example 4 evenly, put it into a crucible, place it in a quartz glass tube with a size of Φ25 mm×240 mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in the crucible descent furnace, and slowly raise the temperature to 515 °C to melt the raw materials;

[0162] b. After the raw materials are completely melted, lower the crucible furnace vertically at a speed of 1 mm / h. During the descent, grow the mercury selenide phosphide crystal. The growth period is 15 days. After the crystal growth is completed, leave the crystal in the crucible descent furnace for annealing, and cool it to room temperature at a rate of 40 °C / h to obtain a black Hg with a size of Φ3.6×2.8 mm. 7 P 2 Se 12 Infrared nonlinear optical crystal.

[0163] Example 35

[0164] The growth of mercury selenide phosphide infrared nonlinear optical crystal by the Bridgman method is carried out according to the following steps:

[0165] a. After grinding 5 g of the pure-phase compound mercury selenide phosphide powder obtained in Example 5 evenly, put it into a crucible, place it in 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 Bridgman furnace, and slowly raise the temperature to 520°C to melt the raw materials;

[0166] b. After the raw materials are completely melted, lower the Bridgman furnace vertically at a speed of 1 mm / h. During the lowering process, grow the mercury selenide phosphide crystal. The growth period is 15 days. After the crystal growth is completed, leave the crystal in the Bridgman furnace for annealing, and cool it to room temperature at a rate of 55°C / h to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0167] Example 36

[0168] The growth of mercury selenide phosphide infrared nonlinear optical crystal by the Bridgman method is carried out according to the following steps:

[0169] a. After grinding 5 g of the pure-phase compound mercury selenide phosphide powder obtained in Example 6 evenly, put it into a crucible, place it in 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 Bridgman furnace, and slowly raise the temperature to 535°C to melt the raw materials;

[0170] b. After the raw materials are completely melted, lower the Bridgman furnace vertically at a speed of 1 mm / h. During the lowering process, grow the mercury selenide phosphide crystal. The growth period is 15 days. After the crystal growth is completed, leave the crystal in the Bridgman furnace for annealing, and cool it to room temperature at a rate of 60°C / h to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0171] Example 37

[0172] The growth of mercury selenide phosphide infrared nonlinear optical crystal by the Bridgman method is carried out according to the following steps:

[0173] a. According to the reaction formula 7Hg + 2P + 12Se = Hg 7 P 2 Se12 , directly mix 1.404 g of Hg, 0.062 g of P and 0.948 g of Se (i.e., Hg:P:Se = 0.007 mol:0.002 mol:0.012 mol) evenly, put them into a crucible, place the crucible in a quartz glass tube with a diameter of Φ25 mm × 240 mm, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a crucible lowering furnace, and slowly raise the temperature to 550 °C to melt the raw materials;

[0174] b. After the raw materials are completely melted, lower the crucible lowering furnace vertically at a speed of 1 mm / h. During the lowering process, carry out Hg 7 P 2 Se 12 crystal growth. The growth period is 20 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 50 °C / h to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0175] Example 38

[0176] The growth of mercury selenide phosphide infrared nonlinear optical crystal by the crucible lowering method is specifically operated according to the following steps:

[0177] a. According to the reaction formula 7Hg + P 2 Se 5 + 7Se = Hg 7 P 2 Se 12 , directly mix 1.404 g of Hg, 0.455 g of P 2 Se 5 and 0.553 g of Se (i.e., Hg:P 2 Se 5 :Se = 0.007 mol:0.001 mol:0.007 mol) evenly, place them in a quartz glass tube with a diameter of Φ25 mm × 240 mm, and put the quartz tube into a programmable temperature-controlled muffle furnace. Heat it to 450 °C at a rate of 10 °C / h, keep it at a constant temperature for 60 h, then cool it to 300 °C at a rate of 10 °C / h. After cooling, take out the sample, crush and grind it to obtain Hg 7 P 2 Se 12 powder, then put it into a quartz tube again, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a crucible lowering furnace, heat it to 480 °C at a rate of 5 °C / h, and keep it at a constant temperature for 60 h until the raw materials are melted;

[0178] b. After the raw materials are completely melted, lower the crucible furnace vertically at a speed of 0.1 mm / h. During the lowering process, carry out Hg 7 P 2 Se 12 crystal growth. The growth period is 22 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 40 °C / h to obtain a Φ2.5×2 mm black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0179] Example 39

[0180] For the growth of mercury selenide phosphide infrared nonlinear optical crystal by the Bridgman method, the specific operation is carried out according to the following steps:

[0181] a. According to the reaction formula 7HgSe + P 2 Se 5 = Hg 7 P 2 Se 12 , directly put 3.206 grams of HgSe and 0.455 grams of P 2 Se 5 (i.e., HgSe:P 2 Se 5 = 0.007 mol:0.001 mol), after mixing evenly, put them into a clean graphite crucible, put the graphite crucible into a Φ25 mm×240 mm quartz tube, and use a vacuum pump to pump the quartz tube to 10 -3 Pa, then carry out melting and sealing, and put the quartz tube into a programmable temperature-controlled muffle furnace, and heat it to 450 °C at a rate of 10 °C / h, and keep it at a constant temperature for 80 h until the raw materials are melted.

[0182] b. After the raw materials are completely melted, lower the crucible furnace vertically at a speed of 0.5 mm / h. During the lowering process, carry out Hg 7 P 2 Se 12 crystal growth. The growth period is 30 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 45 °C / h to obtain a Φ2×1 mm black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0183] Example 40

[0184] For the growth of mercury selenide phosphide infrared nonlinear optical crystal by the Bridgman method, the specific operation is carried out according to the following steps:

[0185] a. According to the reaction formula 7HgSe + 2P + 5Se = Hg 7 P 2 Se 12 , directly mix 1.404 g of HgSe, 0.062 g of P, and 0.395 g of Se (i.e., HgSe:P:Se = 0.007 mol:0.002 mol:0.005 mol) evenly, put them into a clean graphite crucible, place the graphite crucible into a quartz tube with Φ25mm×240mm, and use a vacuum pump to evacuate the quartz tube to 10 -3 Pa, then carry out melting and sealing, and put the quartz tube into a programmable temperature-controlled muffle furnace, heat it to 550°C at a rate of 40°C / h, keep it at a constant temperature for 100 h, then cool it to 300°C at a rate of 20°C / h. After cooling, take out the sample and crush and grind it to obtain Hg 7 P 2 Se 12 powder, then load it into a quartz tube, evacuate it to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a crucible lowering furnace, heat it to 560°C at a rate of 20°C / h, and keep it at a constant temperature for 100 h until the raw materials melt;

[0186] b. After the raw materials are completely melted, lower the crucible lowering furnace vertically at a speed of 2 mm / h. During the lowering process, carry out Hg 7 P 2 Se 12 crystal growth. The growth period is 30 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 45°C / h to obtain a Φ2×1mm black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0187] Example 41

[0188] The growth of mercury selenide phosphide infrared nonlinear optical crystal by the crucible lowering method is carried out according to the following specific steps:

[0189] a. According to the reaction formula 21Hg 2 Cl 2 + 12P + 72Se = 6Hg 7 P 2 Se 12 + 14PCl 3 , directly mix 9.889 g of Hg 2 Cl 2 , 0.372 g of P, and 5.692 g of Se (i.e., Hg 2 Cl 2:P:Se = 0.021 mol:0.012 mol:0.072 mol), after uniform mixing, put it into a clean graphite crucible, place the graphite crucible into a quartz tube with Φ25 mm × 240 mm, and use a vacuum pump to evacuate the quartz tube to 10 -3 Pa, then carry out melting and sealing, and put the quartz tube into a programmable temperature-controlled muffle furnace, heat it up to 500 °C at a rate of 25 °C / h, and keep it at a constant temperature for 80 h until the raw materials melt;

[0190] b. After the raw materials are completely melted, lower the crucible vertically in the furnace at a speed of 3 mm / h, and carry out Hg 7 P 2 Se 12 crystal growth during the descent. The growth period is 40 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 55 °C / h to obtain a Φ5 × 5 mm black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0191] Example 42

[0192] The method for growing mercury cadmium telluride infrared nonlinear optical crystal by the crucible descent method is specifically operated according to the following steps:

[0193] a. According to the reaction formula 21HgI + 6P + 36Se = 3Hg 7 P 2 Se 12 + 7PI 3 , directly put 9.548 g of HgI, 0.186 g of P, and 2.846 g of Se (i.e., HgI:P:Se = 0.021 mol:0.006 mol:0.036 mol), after uniform mixing, put it into a clean graphite crucible, place the graphite crucible into a quartz tube with Φ25 mm × 240 mm, and use a vacuum pump to evacuate the quartz tube to 10 -3 Pa, then carry out melting and sealing, and put the quartz tube into a programmable temperature-controlled muffle furnace, heat it up to 550 °C at a rate of 35 °C / h, keep it at a constant temperature for 90 h, then cool it to 300 °C at a rate of 20 °C / h. After cooling, take out the sample and crush and grind it to obtain Hg 7 P 2 Se 12 powder, then load it into a quartz tube, evacuate it to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a crucible lowering furnace, heat it up to 560 °C at a rate of 5 °C / h, and keep it at a constant temperature for 90 h until the raw materials melt;

[0194] b. After the raw materials are completely melted, lower the crucible vertically in the furnace at a speed of 2 mm / h, and carry out Hg7 P 2 Se 12 Crystal growth, with a growth period of 35 days. After the crystal growth is completed, the crystal is left in the crucible drop furnace for annealing and cooled to room temperature at a rate of 50 °C / h to obtain a black Hg with a size of Φ4×2 mm 7 P 2 Se 12 Infrared nonlinear optical crystal

[0195] Example 43

[0196] The growth of mercury selenide phosphide infrared nonlinear optical crystal by the flux method is carried out according to the following steps:

[0197] Mix 5 g of the pure compound obtained in Example 1 with 2.5 g of the flux Hg 2 Cl 2 in a mass ratio of 1:0.5, and load them into a quartz tube with a diameter of 35 mm and a length of 200 mm. Use a vacuum pump to evacuate the quartz tube to 10 -3 Pa, then perform melting and sealing. Place the sealed quartz tube in a programmable temperature-controlled muffle furnace, heat it to 430 °C, keep it at a constant temperature for 30 h, and then cool it to room temperature at a cooling rate of 2 °C / h to obtain a black Hg with a size of Φ5×3 mm 7 P 2 Se 12 Infrared nonlinear optical crystal

[0198] Example 44

[0199] The growth of mercury selenide phosphide infrared nonlinear optical crystal by the flux method is carried out according to the following steps:

[0200] Mix 5 g of the pure compound obtained in Example 2 with 5 g of the flux Se in a mass ratio of 1:1, load them into a quartz glass tube with a diameter of Φ35 mm×200 mm, use a vacuum pump to evacuate the quartz tube to 10 -3 Pa, then perform melting and sealing. Place the sealed quartz tube in a programmable temperature-controlled muffle furnace, heat it to 450 °C, keep it at a constant temperature for 50 h, and then cool it to room temperature at a cooling rate of 5 °C / h to obtain a black Hg with a size of Φ10×5 mm 7 P 2 Se 12 Infrared nonlinear optical crystal

[0201] Example 45

[0202] The growth of mercury selenide phosphide infrared nonlinear optical crystal by the flux method is carried out according to the following steps:

[0203] Mix 5 g of the pure compound obtained in Example 3 with 10 g of the flux HgSe in a mass ratio of 1:2, and load them into a quartz tube with a diameter of Φ35 mm and a length of 200 mm. Use a vacuum pump to evacuate the quartz tube to 10 -3 Pa, perform melting and sealing. Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it to 480 °C, keep it at a constant temperature for 68 h, and then cool it to room temperature at a cooling rate of 9 °C / h to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal;

[0204] Example 46

[0205] For the growth of mercury selenide phosphide infrared nonlinear optical crystals by the flux method, the specific operation is carried out according to the following steps:

[0206] Mix 1.2 g of mercury selenide phosphide powder obtained in Example 4 with 3.6 g of the flux Hg 2 Cl 2 in a mass ratio of 1:3, and load them into a quartz tube with a diameter of Φ35 mm and a length of 200 mm. Use a vacuum pump to evacuate the quartz tube to 10 -3 Pa, perform melting and sealing. Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it to 460 °C, keep it at a constant temperature for 48 h, and then cool it to room temperature at a cooling rate of 5 °C / h to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0207] Example 47

[0208] For the growth of mercury selenide phosphide infrared nonlinear optical crystals by the flux method, the specific operation is carried out according to the following steps:

[0209] Mix 1.0 g of mercury selenide phosphide powder obtained in Example 5 with 4.0 g of the flux Hg 2 Cl 2 in a mass ratio of 1:4, and load them into a quartz tube with a diameter of Φ35 mm and a length of 200 mm. Use a vacuum pump to evacuate the quartz tube to 10 -3 Pa, perform melting and sealing. Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it to 470 °C, keep it at a constant temperature for 55 h, and then cool it to room temperature at a cooling rate of 7 °C / h to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

[0210] Example 48

[0211] The method for growing HgPSe infrared nonlinear optical crystal by flux method is specifically operated according to the following steps:

[0212] Mix 1.2 g of HgPSe powder of Compound obtained in Example 6 and 5.4 g of flux Se according to the mass ratio of 1:4.5, and load them into a quartz tube with Φ35mm×200mm. Use a vacuum pump to evacuate the quartz tube to 10 -3 Pa, then conduct melting and sealing. Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, and heat it to 480°C. After maintaining the constant temperature for 30 h, cool it to room temperature at a cooling rate of 9°C / h, and then a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal can be obtained.

[0213] Example 49

[0214] Put any one of the Hg 7 P 2 Se 12 infrared nonlinear optical crystals obtained in Examples 7 - 43 at the position labeled 3 in the Figure 3 shown device. At room temperature, use a Q-switched Ho:Tm:Cr:YAG laser as the light source, with an incident infrared light wavelength of 2090 nm, and the output second harmonic generation light wavelength is 1045 nm. The laser intensity output by the Hg 7 P 2 Se 12 crystal is equivalent to the output intensity of AgGaS 2 under the same conditions.

[0215] Example 50

[0216] Put any one of the Hg 7 P 2 Se 12 infrared nonlinear optical crystals obtained in Examples 7 - 43 at the position of 3 as shown. Among them, 1 is a laser, 2 is a convex lens, Hg Figure 3 P 7 P 2 Se 12 infrared nonlinear optical crystal, 4 is a prism, 5 is a filter; the laser beam emitted by the laser 1 passes through the convex lens 2 and then enters the Hg 7 P 2 Se 12 crystal 3, and the generated output laser beam passes through the prism 4 and the filter 5, so as to obtain the required laser beam.

[0217] Using the Hg 7 P 2 Se 12Devices made of infrared nonlinear optical crystals can be frequency doubling generators, up and down frequency converters, optical parametric oscillators, and optical parametric amplifiers.

[0218] The above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit them. Although the present invention has been described in detail with reference to the embodiments, those of ordinary skill in the art should understand that any modification or equivalent replacement of the technical solutions of the present invention does not depart from the spirit and scope of the technical solutions of the present invention.

Claims

1. A compound of selenium, phosphorus and mercury, characterized in that The molecular formula of this compound is Hg 7 P 2 Se 12 , with a molecular weight of 2413.

59. It has a crystal structure, belonging to the triclinic system, and the space group is P 1, and it is prepared by the high-temperature melt method.

2. The preparation method of the compound of selenium, phosphorus and mercury according to claim 1, characterized in that It is carried out according to the following steps: a. According to the molar ratio Hg∶P∶Se = 7∶2∶12, using Hg, Hg 2 Cl 2 、HgI 2 or HgSe as the Hg source material; P or P 2 Se 5 as the P source material, and Se as the selenium source material, mix them evenly to obtain a mixture; b. Grind the mixture obtained in step a to 100 mesh, put it into a quartz container, and evacuate it to 10 -3 Pa for melting and sealing; c. Place the sealed sample in step b in a muffle furnace, heat it at a rate of 10 - 40 °C / h to 450 - 550 °C, keep it at a constant temperature for 40 - 60 h, then cool it to 300 °C at a rate of 10 - 20 °C / h. After cooling, take out the sample and crush and grind it to 100 mesh to obtain a powdery pure sample of selenium, phosphorus and mercury.

3. A selenium, phosphorus and mercury infrared nonlinear optical crystal, characterized in that, The crystal has a molecular formula of Hg 7 P 2 Se 12 , a molecular weight of 2413.59, no center of symmetry, belonging to the triclinic crystal system, and the space group is P 1. The unit cell parameters are a = 12.573(2) Å, b = 14.523(2) Å, c = 16.247(2) Å, α = 77.509(5)°, β = 75.191(6)°, γ = 73.051(5)°, and Z = 5.

4. The preparation method of the selenium, phosphorus and mercury 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, flux method or Bridgman method: For growing the selenium, phosphorus and mercury infrared nonlinear optical crystal by the high-temperature melt method, the specific operation is carried out according to the following steps: a. Mix the Hg source material, P source material, and elemental Se evenly in a molar ratio of Hg∶P∶Se = 7∶2∶12, grind to 100 mesh, load into a quartz tube, evacuate to 10 -3 Pa and seal it. Place it in a muffle furnace, heat it at a rate of 10 - 40 °C / h to 450 - 550 °C, keep it at a constant temperature for 60 - 100 h, cool it to 300 °C at a rate of 10 - 20 °C / h. After cooling, take out the sample and crush and grind it to obtain powdered Hg 7 P 2 Se 12 compound, where the Hg source material is Hg, Hg 2 Cl 2 、HgI 2 or HgSe; the P source material is P or P 2 Se 5 , and the selenium source material is Se; b. Load the compound powder into a quartz tube, evacuate to 10 -3 Pa, seal with a hydrogen-oxygen flame, place in a muffle furnace, slowly heat to 450 - 500 °C, keep at a constant temperature for 24 - 72 h, then slowly cool to room temperature at a rate of 1 - 5 °C / h, turn off the muffle furnace, cut the quartz tube after cooling to obtain black Hg 7 P 2 Se 12 Infrared nonlinear optical crystal; For growing the selenium, phosphorus and mercury infrared nonlinear optical crystal by the chemical vapor transport method, the specific operation is carried out according to the following steps: a. Mix the Hg source material, P source material and elemental Se evenly according to the molar ratio of Hg∶P∶Se = 7∶2∶12, then load them into a quartz tube, evacuate to 10 -3 Pa, seal with a hydrogen-oxygen flame, and place it in a tube furnace, where the Hg source material is Hg, Hg 2 Cl 2 、HgI 2 or HgSe; the P source material is P or P 2 Se 5 , and the Se source material is Se; b. Carry out chemical vapor transport in a tubular growth furnace, and grow the crystals of Hg 7 P 2 Se 12 by means of a horizontal or vertical gradient temperature field. Heat it up to 450 - 550 °C at a rate of 25 °C / h, with a growth period of 8 - 20 days. After the growth is completed, slowly cool it down to room temperature at a rate of 1 - 5 °C / h, turn off the tubular growth furnace. After the quartz tube cools down, cut it open to obtain black Hg 7 P 2 Se 12 infrared nonlinear optical crystal; For growing the selenium, phosphorus and mercury infrared nonlinear optical crystal by the flux method, the specific operation is carried out according to the following steps: a. Mix the Hg source material, P source material, and Se source material evenly in a molar ratio of 6.5 - 8:2:12 - 14, place them in a clean graphite crucible, put the graphite crucible into a quartz tube, and use a vacuum pump to pump the quartz tube to 10 -3 Pa, then carry out melting and sealing, and place the quartz tube in a programmable temperature-controlled muffle furnace. Heat it at a rate of 10 - 40 °C / h to 450 - 550 °C, keep the temperature constant for 60 - 100 h, cool it to 300 °C at a rate of 10 - 20 °C / h. After cooling, take out the sample and crush and grind it to obtain Hg 7 P 2 Se 12 powdery, where the Hg source material is Hg, Hg 2 Cl 2 、HgI 2 or HgSe; the P source material is P or P 2 Se 5 , and the selenium source material is Se; b. Mix the selenium-phosphorus-mercury powder obtained in step a with a flux of Se, HgSe or Hg in a mass ratio of 1:0.5 - 4.5 2 Cl 2 and load it into a quartz tube with a diameter of 35 mm and a length of 20 cm. Use a vacuum pump to evacuate the quartz tube to 10 -3 Pa, then perform melting and sealing. Place the sealed quartz tube into a programmable temperature-controlled muffle furnace and heat it to 430 - 480 °C, keep it at a constant temperature for 30 - 68 h, and then cool it to room temperature at a cooling rate of 2 - 9 °C / h to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal; For growing the selenium, phosphorus and mercury infrared nonlinear optical crystal by the Bridgman method, the specific operation is carried out according to the following steps: a. Mix the Hg source material, P source material, and Se source material evenly in a molar ratio of 6.5 - 8:2:12 - 14, put them into a clean graphite crucible, place the graphite crucible into a quartz tube, and use a vacuum pump to evacuate the quartz tube to 10 -3 Pa. Then, perform melting and sealing, and place the quartz tube into a programmable temperature-controlled muffle furnace. Heat it at a rate of 10 - 40 °C / h to 450 - 550 °C, keep it at a constant temperature for 60 - 100 h, then cool it to 300 °C at a rate of 10 - 20 °C / h. After cooling, take out the sample, crush and grind it to obtain powdered Hg 7 P 2 Se 12 , then put it back into the quartz tube, evacuate to 10 -3 Pa, seal it with a hydrogen-oxygen flame, place it in a crucible lowering furnace, heat it at a rate of 5 - 20 °C / h to 480 - 560 °C, and keep it at a constant temperature for 60 - 100 h until the raw materials melt; Mix the Hg source material, P source material, and Se source material evenly in a molar ratio of 6.5 - 8:2:12 - 14, put them into a clean graphite crucible, place the graphite crucible into a quartz tube, and use a vacuum pump to evacuate the quartz tube to 10 -3 Pa, then conduct melting and sealing, and place the quartz tube into a programmable temperature-controlled crucible drop furnace, heat it at a rate of 10 - 40 °C / h to 450 - 550 °C, and keep the temperature constant for 60 - 100 h until the raw materials melt, where the Hg source material is Hg, Hg 2 Cl 2 、HgI 2 or HgSe; the P source material is P or P 2 Se 5 , and the selenium source material is Se; b. After the raw materials are completely melted, lower the crucible furnace vertically at a rate of 0.1 - 3 mm / h, and conduct Hg 7 P 2 Se 12 crystal growth during the lowering process. The growth period is 20 - 40 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 40 - 60 °C / h to obtain a black Hg 7 P 2 Se 12 infrared nonlinear optical crystal.

5. Use of the selenium, phosphorus and mercury infrared nonlinear optical crystal according to 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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