Compounds of gallium selenide, mercury-magnesium selenide and infrared nonlinear optical crystals of gallium selenide, mercury-magnesium selenide, their preparation methods and applications

Abstract

This invention relates to a compound, magnesium gallium selenide (MgHgGa4Se8), and a magnesium gallium selenide (MgHgGa4Se8) infrared nonlinear optical crystal, along with their preparation methods and applications. The compound has the molecular formula MgHgGa4Se8 and a molecular weight of 1135.46 g / mol. The crystal, also with the molecular formula MgHgGa4Se8 and a molecular weight of 1135.46 g / mol, lacks a center of symmetry, belongs to the tetragonal crystal system, and has a space group of MgHgGa4Se8. Its cell parameters are α = β = γ = 90°, Z = 1, and its volume is determined by the high-temperature melt method, chemical vapor transport method, or crucible lowering method. This crystal exhibits advantages such as significant nonlinear optical effects, good crystal growth habit, good mechanical properties, high hardness, resistance to breakage and deliquescence, and ease of processing and storage. It can be used to fabricate infrared nonlinear optical devices, which have important applications in optoelectronic warfare, laser communication, and medical fields.

Description

Technical Field

[0001] This invention belongs to the field of infrared nonlinear optical crystal preparation, specifically relating to magnesium gallium selenide (MgHgGa4Se8) compounds, magnesium gallium selenide infrared nonlinear optical crystals, their preparation methods, and applications. Background Technology

[0002] Nonlinear optical crystals are a class of crystal materials exhibiting nonlinear optical effects such as frequency doubling, sum-frequency generation, difference-frequency generation, and optical parametric amplification. Only crystals with asymmetry centers can produce second-order nonlinear optical effects. Utilizing 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 fabricated. Lasers generated by lasers can undergo frequency conversion through nonlinear optical devices, thereby obtaining more new laser sources and driving the development of laser technology. Based on the different application wavelengths, nonlinear optical crystal materials can be divided into three main categories: ultraviolet nonlinear optical materials, visible and near-infrared nonlinear optical materials, and mid- and far-infrared nonlinear optical materials. Among these, 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 (532nm) crystals, KTP (KTiOPO4), β-BBO (β-BaB2O4), and LBO (LiB3O5) crystals are commonly used; in deep ultraviolet crystals, KBBF (KBe2BO3F2) and ABF (NH4B4O6F) are available options. The development of nonlinear crystals in the mid- and far-infrared bands has been relatively slow. Currently, most commercially available mid- and far-infrared nonlinear optical materials are chalcopyrite-structured semiconductor materials, such as AgGaQ2 (Q = S, Se) and ZnGeP2. However, most of these mid- and far-infrared nonlinear optical materials were developed around the 1970s. Due to some intrinsic performance defects, such as a low laser damage threshold, a narrow bandgap, and two-photon absorption near 1 μm, the application of these materials in the current high-power laser output field is greatly limited, and they can no longer fully meet the application requirements of current laser technology development. There is an urgent need to develop new mid- and far-infrared nonlinear optical crystal materials with balanced performance. Summary of the Invention

[0003] The purpose of this invention is to provide a compound with the chemical formula MgHgGa4Se8, which has a molecular weight of 1135.46 g / mol, and is prepared by a high-temperature solid-state method.

[0004] Another objective of this invention is to provide a MgHgGa4Se8 infrared nonlinear optical crystal. This crystal has the molecular formula MgHgGa4Se8, a molecular weight of 1135.46 g / mol, lacks a center of symmetry, belongs to the tetragonal crystal system, and has a space group of [missing information]. The unit cell parameters are: α=β=γ=90°, Z=1, volume is

[0005] Another objective of this invention is to provide a method for preparing MgHgGa4Se8 nonlinear optical crystals.

[0006] Another object of the present invention is to provide the use of MgHgGa4Se8 nonlinear optical crystals.

[0007] The present invention discloses a compound, magnesium selenide gallium mercury, with the molecular formula MgHgGa4Se8 and a molecular weight of 1135.46 g / mol. It belongs to the tetragonal crystal system and crystallizes in the non-central space group. It is produced by high-temperature solid-state method.

[0008] The preparation method of the compound magnesium selenide gallium mercury, with the molecular formula MgHgGa4Se8, is carried out by a high-temperature solid-state method, and the specific operation is as follows:

[0009] a. Using a molar ratio of Mg:Hg:Ga:Se = 1:1:4:8, mix Mg or MgSe (Mg source material), Hg or HgSe (Hg source material), and Ga, GaSe or Ga2Se3 (Ga source material) with elemental Se until homogeneous. Grind the mixture and place it into a 25mm × 240mm quartz container. Evacuate the container to 100°C. -3 -10 -5 Pa and perform melt sealing;

[0010] b. Place the sealed sample from step a in a muffle furnace and heat it to 800-920℃ at a rate of 10-40℃ / h. Hold the temperature for 60-80 hours, then reduce the temperature to 400℃ at a rate of 10-20℃ / h. Allow it to cool naturally to room temperature. After cooling, remove the sample and crush and grind it to obtain powdered MgHgGa4Se8 compound.

[0011] A selenium-gallium-mercury-magnesium infrared nonlinear optical crystal, with the molecular formula MgHgGa4Se8 and a molecular weight of 1135.46 g / mol, lacks a center of symmetry, belongs to the tetragonal crystal system, and has a space group of [missing information]. Cell parameters are α=β=γ=90°, Z=1.

[0012] The method for preparing the selenium gallium mercury magnesium infrared nonlinear optical crystal employs a high-temperature melt method, a chemical vapor transport method, or a crucible lowering method for crystal growth.

[0013] The high-temperature melt method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is carried out according to the following steps:

[0014] a. Using a molar ratio of Mg:Hg:Ga:Se = 1:1:4:8, mix Mg or MgSe as the Mg source material; Hg or HgSe as the Hg source material; and Ga, GaSe, or Ga2Se3 as the Ga source material with elemental Se until homogeneous. Then, pack the mixture into a 25mm × 240mm quartz tube and evacuate to 100°C. -3 -10 -5 Pa was sealed and placed in a muffle furnace. The temperature was increased to 800-920℃ at a rate of 10-40℃ / h and held at that temperature for 60-80h. The temperature was then reduced to 400℃ at a rate of 10-20℃ / h. After cooling to room temperature naturally, the sample was removed, crushed, and ground to obtain a powdered pure MgHgGa4Se8 sample.

[0015] b. Place the obtained pure sample powder into a quartz tube and evacuate to 10°C. -3 -10 -5 Pa was encapsulated in an oxyhydrogen flame, placed in a muffle furnace, and slowly heated to 930-1000℃, held at that temperature for 48-72 hours, then slowly cooled to 800℃ at a rate of 1-5℃ / h, and then cooled to room temperature at a rate of 10-20℃ / h. The muffle furnace was then turned off, and the quartz tube was cut open after cooling to obtain a red MgHgGa4Se8 infrared nonlinear optical crystal.

[0016] The chemical vapor transport method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is performed according to the following steps:

[0017] a. Using a molar ratio of Mg:Hg:Ga:Se = 1:1:4:8, mix Mg or MgSe as the Mg source material; Hg or HgSe as the Hg source material; and Ga, GaSe, or Ga2Se3 as the Ga source material with elemental Se until homogeneous. Then, pack the mixture into a 25mm × 240mm quartz tube and evacuate to 100°C. -3 -10 -5 Pa was encapsulated in an oxyhydrogen flame, placed in a muffle furnace, heated to 800-920℃ at a rate of 10-40℃ / h, held at the temperature for 60-80h, and then cooled to 400℃ at a rate of 10-20℃ / h. After that, the sample was naturally cooled to room temperature, removed, and crushed and ground to obtain a pure powder of MgHgGa4Se8.

[0018] b. The obtained pure sample powder is mixed with element I and chemical vapor transport is carried out in a tube growth furnace, where the high temperature zone is 950-1100℃ and the low temperature zone is 800-900℃. MgHgGa4Se8 crystals are grown through a horizontal or vertical gradient temperature field. The temperature is simultaneously raised to 950-1100℃ in the high temperature zone and 800-900℃ in the low temperature zone at a rate of 15-25℃ / h. The growth cycle is 15-35 days. After the growth is completed, the temperature is slowly reduced to room temperature at a rate of 2-9℃ / h. The tube growth furnace is then turned off. After the quartz tube cools down, it is cut open to obtain a red MgHgGa4Se8 infrared nonlinear optical crystal at the low temperature end.

[0019] The crucible lowering method for growing selenium-gallium-mercury-magnesium infrared nonlinear optical crystals is performed according to the following steps:

[0020] a. Using a molar ratio of Mg:Hg:Ga:Se = 1:1:4:8, mix Mg or MgSe as the Mg source material; Hg or HgSe as the Hg source material; and Ga, GaSe, or Ga2Se3 as the Ga source material with elemental Se until homogeneous. Then, pack the mixture into a 25mm × 240mm quartz tube and evacuate to 100°C. -3 -10 -5 Pa was encapsulated in an oxyhydrogen flame, placed in a muffle furnace, heated to 800-920℃ at a rate of 10-40℃ / h, held at the temperature for 60-80h, and then cooled to 400℃ at a rate of 10-20℃ / h. After that, the sample was naturally cooled to room temperature, removed, and crushed and ground to obtain a pure powder of MgHgGa4Se8.

[0021] b. Place the obtained pure sample powder into a quartz tube and evacuate to 10°C. -3 -10 -5 Pa is encapsulated in an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature is increased to 940-1000℃ at a rate of 5-20℃ / h and held at that temperature for 60-100h until the raw material is completely melted. The crucible lowering furnace is then lowered vertically at a rate of 1-3mm / h, during which crystal growth takes place. The growth cycle is 15-25 days. After the crystal growth is completed, the crystal is left in the crucible lowering furnace for annealing and then cooled to room temperature at a rate of 20-40℃ / h to obtain a red MgHgGa4Se8 infrared nonlinear optical crystal.

[0022] The selenium gallium mercury magnesium infrared nonlinear optical crystal is used in the preparation of infrared band laser frequency conversion crystals, infrared all-solid-state lasers, infrared electro-optic devices, infrared communication devices, or infrared laser guidance devices.

[0023] The preparation methods of the selenium gallium mercury magnesium infrared nonlinear optical crystals described in this invention can all obtain MgHgGa4Se8 nonlinear optical crystals with a size in the centimeter range; by using a large-size crucible and extending the growth time, a correspondingly larger MgHgGa4Se8 nonlinear optical crystal can be obtained.

[0024] The selenium gallium mercury magnesium infrared nonlinear optical crystal of the present invention has the advantages of low synthesis temperature and no inclusions, low cost, and easy acquisition of large-size crystals; the obtained selenium gallium mercury magnesium infrared nonlinear optical crystal and device have the advantages of laser damage resistance, large nonlinear optical effect, wide transmission band, high hardness, good mechanical properties, not easy to break and deliquesce, and easy to process and store; the MgHgGa4Se8 nonlinear optical crystal can be used to make infrared nonlinear optical devices.

[0025] Based on the crystallographic data of the crystal, the crystal blank is oriented, and the crystal is cut according to the required angle, thickness and cross-sectional size. The light-transmitting surface of the crystal is polished, and it can then be used as a nonlinear optical device.

[0026] The application of the selenium gallium mercury magnesium infrared nonlinear optical crystal described in this invention in the field of laser technology includes its use in the preparation of infrared band laser frequency conversion crystals, infrared lasers, infrared electro-optic devices, infrared communication devices, or infrared laser guidance devices.

[0027] The compound MgHgGa4Se8 described in this invention can be prepared according to the following chemical reaction formula:

[0028] (1)Mg+Hg+4Ga+8Se=MgHgGa4Se8;

[0029] (2)Mg+Hg+4GaSe+4Se=MgHgGa4Se8;

[0030] (3)Mg+Hg+2Ga2Se3+2Se=MgHgGa4Se8;

[0031] (4)Mg+HgSe+4Ga+7Se=MgHgGa4Se8;

[0032] (5)Mg+HgSe+4GaSe+3Se=MgHgGa4Se8;

[0033] (6)Mg+HgSe+2Ga2Se3+Se=MgHgGa4Se8;

[0034] (7)MgSe+Hg+4Ga+7Se=MgHgGa4Se8;

[0035] (8)MgSe+Hg+4GaSe+3Se=MgHgGa4Se8;

[0036] (9)MgSe+Hg+2Ga2Se3+Se=MgHgGa4Se8;

[0037] (10)MgSe+HgSe+4Ga+6Se=MgHgGa4Se8;

[0038] (11)MgSe+HgSe+4GaSe+2Se=MgHgGa4Se8;

[0039] (12)MgSe+HgSe+2Ga2Se3=MgHgGa4Se8. Attached Figure Description

[0040] Figure 1 This is a schematic diagram of the structure of the selenium-gallium-mercury-magnesium crystal of the present invention, wherein magnesium / mercury atoms are tetra-coordinated with selenium atoms to form [(MgHg)Se4] units, and gallium atoms are coordinated with selenium atoms to form [GaSe4] units. Figure 1 a); then, the [(MgHg)Se4] and [GaSe4] units are interconnected through corner sharing and edge sharing to construct a diamond-like three-dimensional structure. Figure 1 be);

[0041] Figure 2 This is a comparison diagram of the X-ray diffraction patterns of polycrystalline powder before and after melting of the selenium gallium mercury magnesium crystal of the present invention with the theoretical values;

[0042] Figure 3 This is a schematic diagram of the second-order NLO effect signal of the crystal of the present invention. The magnesium selenide gallium mercury magnesium exhibits a phase-matched large NLO response, which is about 1.8 times that of the reference AgGaS2.

[0043] Figure 4 This is a schematic diagram of the working principle of the optical device of the present invention, wherein 1 is a laser, 2 is a convex lens, 3 is a MgHgGa4Se8 nonlinear optical crystal after crystal post-processing and optical processing, 4 is a prism, and 5 is a filter. Detailed Implementation

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

[0045] Example 1

[0046] The compound MgHgGa4Se8 was prepared by a high-temperature solid-state method based on the chemical reaction Mg + Hg + 4Ga + 8Se = MgHgGa4Se8. The specific operation is as follows:

[0047] 0.107 g of elemental Mg, 0.883 g of elemental Hg, 1.228 g of elemental Ga, and 2.782 g of elemental Se were mixed thoroughly and placed into a 25 mm × 240 mm quartz glass tube. The quartz tube was then evacuated to 10 °C using a vacuum pump. -3 -10 -5 After achieving a vacuum level of Pa, a melt-sealing process is performed.

[0048] The sealed quartz tube was placed in a temperature-controlled muffle furnace and heated to 800°C at a rate of 40°C / h, held at that temperature for 80h, and then cooled to 400°C at a rate of 20°C / h. After that, the sample was naturally cooled to room temperature and then removed. The sample was then crushed and ground into powder form of selenium gallium mercury magnesium compound.

[0049] Example 2

[0050] The compound MgHgGa4Se8 was prepared by a high-temperature solid-state method based on the chemical reaction Mg + Hg + 4GaSe + 4Se = MgHgGa4Se8. The specific operation is as follows:

[0051] 0.109 g of elemental Mg, 0.896 g of elemental Hg, 2.584 g of compound GaSe, and 1.411 g of elemental Se were mixed thoroughly and placed into a 25 mm × 240 mm quartz glass tube. The quartz tube was then evacuated to 10 °C using a vacuum pump. -3 -10 -5 After achieving a vacuum level of Pa, a melt-sealing process is performed.

[0052] The sealed quartz tube was placed in a temperature-controlled muffle furnace and heated to 820°C at a rate of 36°C / h, held at that temperature for 76h, and then cooled to 400°C at a rate of 18°C / h. After cooling naturally to room temperature, the sample was removed and crushed and ground into powder form of selenium gallium mercury magnesium compound.

[0053] Example 3

[0054] The compound MgHgGa4Se8 was prepared by a high-temperature solid-state method using the chemical reaction Mg + Hg + 2Ga2Se3 + 2Se = MgHgGa4Se8. The specific operation is as follows:

[0055] 0.107 g of elemental Mg, 0.883 g of elemental Hg, 3.314 g of compound Ga₂Se₃, and 0.695 g of elemental Se were mixed thoroughly and placed into a 25 mm × 240 mm quartz glass tube. The quartz tube was then evacuated to 10 °C using a vacuum pump. -3 -10 -5 After achieving a vacuum level of Pa, a melt-sealing process is performed.

[0056] The sealed quartz tube was placed in a temperature-controlled muffle furnace and heated to 840°C at a rate of 32°C / h, held at that temperature for 74h, and then cooled to 400°C at a rate of 16°C / h. After cooling naturally to room temperature, the sample was removed and crushed and ground into powder form of selenium gallium mercury magnesium compound.

[0057] Example 4

[0058] The compound MgHgGa4Se8 was prepared by a high-temperature solid-state method based on the chemical reaction Mg + HgSe + 4Ga + 7Se = MgHgGa4Se8. The specific operation is as follows:

[0059] 0.113 g of elemental Mg, 1.010 g of compound HgSe, 1.300 g of elemental Ga, and 2.577 g of elemental Se were mixed thoroughly and placed into a 25 mm × 240 mm quartz glass tube. The quartz tube was then evacuated to 10 °C using a vacuum pump. -3 -10 -5 After achieving a vacuum level of Pa, a melt-sealing process is performed.

[0060] The sealed quartz tube was placed in a temperature-controlled muffle furnace and heated to 860°C at a rate of 28°C / h, held at that temperature for 72 hours, and then cooled to 400°C at a rate of 14°C / h. After cooling naturally to room temperature, the sample was removed and crushed and ground into powder form of selenium gallium mercury magnesium compound.

[0061] Example 5

[0062] The compound MgHgGa4Se8 was prepared by a high-temperature solid-state method based on the chemical reaction Mg + HgSe + 4GaSe + 3Se = MgHgGa4Se8. The specific operation is as follows:

[0063] 0.115 g of elemental Mg, 1.025 g of compound HgSe, 2.738 g of compound GaSe, and 1.121 g of elemental Se were mixed thoroughly and placed into a 25 mm × 240 mm quartz glass tube. The quartz tube was then evacuated to 10 °C using a vacuum pump. -3 -10 -5 After achieving a vacuum level of Pa, a melt-sealing process is performed.

[0064] The sealed quartz tube was placed in a temperature-controlled muffle furnace and heated to 880°C at a rate of 24°C / h, held at that temperature for 70h, and then cooled to 400°C at a rate of 12°C / h. After cooling naturally to room temperature, the sample was removed and crushed and ground into powder form of selenium gallium mercury magnesium compound.

[0065] Example 6

[0066] The compound MgHgGa4Se8 was prepared by a high-temperature solid-state method based on the chemical reaction Mg + HgSe + 4GaSe + 3Se = MgHgGa4Se8. The specific operation is as follows:

[0067] 0.115 g of elemental Mg, 1.025 g of compound HgSe, 2.738 g of compound GaSe, and 1.121 g of elemental Se were mixed thoroughly and placed into a 25 mm × 240 mm quartz glass tube. The quartz tube was then evacuated to 10 °C using a vacuum pump. -3 -10 -5 After achieving a vacuum level of Pa, a melt-sealing process is performed.

[0068] The sealed quartz tube was placed in a temperature-controlled muffle furnace and heated to 900°C at a rate of 20°C / h, held at that temperature for 68 hours, and then cooled to 400°C at a rate of 10°C / h. After cooling naturally to room temperature, the sample was removed and crushed and ground into powder form of selenium gallium mercury magnesium compound.

[0069] Example 7

[0070] The compound MgHgGa4Se8 was prepared by a high-temperature solid-state method based on the chemical reaction MgSe + Hg + 4Ga + 7Se = MgHgGa4Se8. The specific operation was carried out according to the following steps:

[0071] 0.455 g of compound Mg, 0.883 g of elemental Hg, 1.228 g of elemental Ga, and 2.434 g of elemental Se were mixed thoroughly and placed into a 25 mm × 240 mm quartz glass tube. The quartz tube was then evacuated to 10 °C using a vacuum pump. -3 -10 -5 After achieving a vacuum level of Pa, a melt-sealing process is performed.

[0072] The sealed quartz tube was placed in a temperature-controlled muffle furnace and heated to 900°C at a rate of 18°C / h, held at that temperature for 60h, and then cooled to 400°C at a rate of 10°C / h. After that, the sample was naturally cooled to room temperature and then removed. The sample was then crushed and ground into powder form of selenium gallium mercury magnesium compound.

[0073] Example 8

[0074] The compound MgHgGa4Se8 was prepared by a high-temperature solid-state method based on the chemical reaction MgSe + Hg + 4GaSe + 3Se = MgHgGa4Se8. The specific operation is as follows:

[0075] 0.461 g of compound MgSe, 0.896 g of metallic element Hg, 2.584 g of compound GaSe, and 1.058 g of elemental Se were mixed thoroughly and placed into a 25 mm × 240 mm quartz glass tube. The quartz tube was then evacuated to 10 °C using a vacuum pump. -3-10 -5 After achieving a vacuum level of Pa, a melt-sealing process is performed.

[0076] The sealed quartz tube was placed in a temperature-controlled muffle furnace and heated to 920°C at a rate of 18°C / h, held at that temperature for 66 hours, and then cooled to 400°C at a rate of 10°C / h. After cooling naturally to room temperature, the sample was removed and crushed and ground into powder form of selenium gallium mercury magnesium compound.

[0077] Example 9

[0078] The compound MgHgGa4Se8 was prepared by a high-temperature solid-state method using the chemical reaction MgSe + Hg + 2Ga2Se3 + Se = MgHgGa4Se8. The specific operation is as follows:

[0079] 0.455 g of compound MgSe, 0.883 g of metallic element Hg, 3.314 g of compound Ga2Se3, and 0.348 g of elemental Se were mixed thoroughly and placed into a 25 mm × 240 mm quartz glass tube. The quartz tube was then evacuated to 10 °C using a vacuum pump. -3 -10 -5 After achieving a vacuum level of Pa, a melt-sealing process is performed.

[0080] The sealed quartz tube was placed in a temperature-controlled muffle furnace and heated to 920°C at a rate of 12°C / h, held at that temperature for 60h, and then cooled to 400°C at a rate of 16°C / h. After that, the sample was naturally cooled to room temperature and then removed. The sample was then crushed and ground into powder form of selenium gallium mercury magnesium compound.

[0081] Example 10

[0082] The compound MgHgGa4Se8 was prepared by a high-temperature solid-state method based on the chemical reaction MgSe + HgSe + 4Ga + 6Se = MgHgGa4Se8. The specific operation is as follows:

[0083] 0.481 g of compound MgSe, 1.010 g of compound HgSe, 1.300 g of metallic element Ga, and 2.209 g of elemental Se were mixed thoroughly and placed into a 25 mm × 240 mm quartz glass tube. The quartz tube was then evacuated to 10 °C using a vacuum pump. -3 -10 -5 After achieving a vacuum level of Pa, a melt-sealing process is performed.

[0084] The sealed quartz tube was placed in a temperature-controlled muffle furnace and heated to 900°C at a rate of 16°C / h, held at that temperature for 60h, and then cooled to 400°C at a rate of 10°C / h. After that, the sample was naturally cooled to room temperature and then removed. The sample was then crushed and ground into powder form of selenium gallium mercury magnesium compound.

[0085] Example 11

[0086] The compound MgHgGa4Se8 was prepared by a high-temperature solid-state method using the chemical reaction MgSe + HgSe + 4GaSe + 2Se = MgHgGa4Se8. The specific operation is as follows:

[0087] 0.489 g of compound MgSe, 1.025 g of compound HgSe, 2.738 g of compound GaSe, and 0.747 g of elemental Se were mixed thoroughly and placed into a 25 mm × 240 mm quartz glass tube. The quartz tube was then evacuated to 10 °C using a vacuum pump. -3 -10 -5 After achieving a vacuum level of Pa, a melt-sealing process is performed.

[0088] The sealed quartz tube was placed in a temperature-controlled muffle furnace and heated to 900°C at a rate of 20°C / h, held at that temperature for 60h, and then cooled to 400°C at a rate of 16°C / h. After that, the sample was naturally cooled to room temperature and then removed. The sample was then crushed and ground into powder form of selenium gallium mercury magnesium compound.

[0089] Example 12

[0090] The compound MgHgGa4Se8 was prepared by a high-temperature solid-state method using the chemical reaction MgSe + HgSe + 2Ga2Se3 = MgHgGa4Se8. The specific operation is as follows:

[0091] After thoroughly mixing 0.481 g of compound MgSe, 1.010 g of compound HgSe, and 3.509 g of compound Ga2Se3, the mixture was placed into a 25 mm × 240 mm quartz glass tube. The quartz tube was then evacuated to 10 °C using a vacuum pump. -3 -10 -5 After achieving a vacuum level of Pa, a melt-sealing process is performed.

[0092] The sealed quartz tube was placed in a temperature-controlled muffle furnace and heated to 900°C at a rate of 16°C / h, held at that temperature for 70h, and then cooled to 400°C at a rate of 20°C / h. After cooling naturally to room temperature, the sample was removed and crushed and ground into powder form of selenium gallium mercury magnesium compound.

[0093] Example 13

[0094] The high-temperature melt method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is carried out according to the following steps:

[0095] The pure sample of selenium gallium mercury magnesium powder obtained in Example 1 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5Pa was encapsulated in an oxyhydrogen flame, placed in a muffle furnace, and slowly heated to 930°C, held at that temperature for 72 hours, then slowly cooled to 800°C at a rate of 5°C / hour, and then cooled to room temperature at a rate of 20°C / hour. The muffle furnace was then turned off, and the quartz tube was cut open after cooling to obtain a Φ3×2mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0096] Example 14

[0097] The high-temperature melt method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is carried out according to the following steps:

[0098] The pure sample of selenium gallium mercury magnesium powder obtained in Example 2 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 Pa was encapsulated in an oxyhydrogen flame, placed in a muffle furnace, and slowly heated to 940°C, held at that temperature for 70 hours, then slowly cooled to 800°C at a rate of 5°C / hour, and then cooled to room temperature at a rate of 18°C / hour. The muffle furnace was then turned off, and the quartz tube was cut open after cooling to obtain a Φ3×1mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0099] Example 15

[0100] The high-temperature melt method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is carried out according to the following steps:

[0101] The pure sample of selenium gallium mercury magnesium powder obtained in Example 3 was placed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 Pa was encapsulated in an oxyhydrogen flame, placed in a muffle furnace, and slowly heated to 950°C, held at that temperature for 68 hours, then slowly cooled to 800°C at a rate of 5°C / h, and then cooled to room temperature at a rate of 16°C / h. The muffle furnace was then turned off, and the quartz tube was cut open after cooling to obtain a Φ3×3mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0102] Example 16

[0103] The high-temperature melt method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is carried out according to the following steps:

[0104] The pure sample of selenium gallium mercury magnesium powder obtained in Example 4 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 Pa was encapsulated in an oxyhydrogen flame, placed in a muffle furnace, and slowly heated to 960°C, held at that temperature for 66 hours, then slowly cooled to 800°C at a rate of 4°C / hour, and then cooled to room temperature at a rate of 16°C / hour. The muffle furnace was then turned off, and the quartz tube was cut open after cooling to obtain a Φ5×3mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0105] Example 17

[0106] The high-temperature melt method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is carried out according to the following steps:

[0107] The pure sample of selenium gallium mercury magnesium powder obtained in Example 5 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 Pa was encapsulated in an oxyhydrogen flame, placed in a muffle furnace, and slowly heated to 970°C, held at that temperature for 64 hours, then slowly cooled to 800°C at a rate of 4°C / hour, and then cooled to room temperature at a rate of 16°C / hour. The muffle furnace was then turned off, and the quartz tube was cut open after cooling to obtain a Φ6×3mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0108] Example 18

[0109] The high-temperature melt method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is carried out according to the following steps:

[0110] The pure sample of selenium gallium mercury magnesium powder obtained in Example 6 was placed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 Pa was encapsulated in an oxyhydrogen flame, placed in a muffle furnace, and slowly heated to 980°C, held at that temperature for 62 hours, then slowly cooled to 800°C at a rate of 4°C / hour, and then cooled to room temperature at a rate of 14°C / hour. The muffle furnace was then turned off, and the quartz tube was cut open after cooling to obtain a Φ6×4mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0111] Example 19

[0112] The high-temperature melt method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is carried out according to the following steps:

[0113] The pure sample of selenium gallium mercury magnesium powder obtained in Example 7 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 Pa was encapsulated in an oxyhydrogen flame, placed in a muffle furnace, and slowly heated to 990°C, held at that temperature for 60 hours, then slowly cooled to 800°C at a rate of 3°C / hour, and then cooled to room temperature at a rate of 14°C / hour. The muffle furnace was then turned off, and the quartz tube was cut open after cooling to obtain a Φ4×2mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0114] Example 20

[0115] The high-temperature melt method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is carried out according to the following steps:

[0116] The pure sample of selenium gallium mercury magnesium powder obtained in Example 8 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5Pa was encapsulated in an oxyhydrogen flame, placed in a muffle furnace, and slowly heated to 990°C, held at that temperature for 60 hours, then slowly cooled to 800°C at a rate of 3°C / hour, and then cooled to room temperature at a rate of 12°C / hour. The muffle furnace was then turned off, and the quartz tube was cut open after cooling to obtain a Φ4×3mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0117] Example 21

[0118] The high-temperature melt method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is carried out according to the following steps:

[0119] The pure sample of selenium gallium mercury magnesium powder obtained in Example 9 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 Pa was encapsulated with an oxyhydrogen flame, placed in a muffle furnace, and slowly heated to 1000℃, held at that temperature for 58 hours, then slowly cooled to 800℃ at a rate of 2℃ / h, and then cooled to room temperature at a rate of 10℃ / h. The muffle furnace was then turned off, and the quartz tube was cut open after cooling to obtain a Φ5×3mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0120] Example 22

[0121] The high-temperature melt method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is carried out according to the following steps:

[0122] The pure sample of selenium gallium mercury magnesium powder obtained in Example 10 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 Pa was encapsulated with an oxyhydrogen flame, placed in a muffle furnace, and slowly heated to 1000℃, held at that temperature for 56 hours, then slowly cooled to 800℃ at a rate of 1℃ / h, and then cooled to room temperature at a rate of 10℃ / h. The muffle furnace was then turned off, and the quartz tube was cut open after cooling to obtain a Φ5×4mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0123] Example 23

[0124] The high-temperature melt method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is carried out according to the following steps:

[0125] The pure sample of selenium gallium mercury magnesium powder obtained in Example 11 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 Pa was encapsulated with an oxyhydrogen flame, placed in a muffle furnace, and slowly heated to 1000℃, held at that temperature for 54 hours, then slowly cooled to 800℃ at a rate of 1℃ / h, and then cooled to room temperature at a rate of 12℃ / h. The muffle furnace was then turned off, and the quartz tube was cut after cooling to obtain a Φ6×4mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0126] Example 24

[0127] The high-temperature melt method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is carried out according to the following steps:

[0128] The pure sample of selenium gallium mercury magnesium powder obtained in Example 12 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 Pa was encapsulated with an oxyhydrogen flame, placed in a muffle furnace, and slowly heated to 1000℃, held at that temperature for 50 hours, then slowly cooled to 800℃ at a rate of 1℃ / h, and then cooled to room temperature at a rate of 15℃ / h. The muffle furnace was then turned off, and the quartz tube was cut open after cooling to obtain a Φ6×3mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0129] Example 25

[0130] The chemical vapor transport method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is performed according to the following steps:

[0131] The pure sample of selenium gallium mercury magnesium powder obtained in Example 1 was mixed with element I and placed in a 25mm × 240mm quartz tube, and the tube was evacuated to 10°C. -5 The sample was encapsulated in an oxyhydrogen flame and placed in a tube furnace for chemical vapor transport at a high temperature of 950°C and a low temperature of 800°C. MgHgGa4Se8 crystals were grown using a horizontal gradient temperature field. The temperature was simultaneously increased to 950°C in the high temperature zone and 800°C in the low temperature zone at a rate of 15°C / h for a growth period of 15 days. After growth, the temperature was slowly reduced to room temperature at a rate of 2°C / h, the tube furnace was shut off, and the quartz tube was cut after cooling. A Φ5.2×3.3mm red selenium gallium mercury magnesium infrared nonlinear optical crystal was obtained at the low temperature end.

[0132] Example 26

[0133] The chemical vapor transport method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is performed according to the following steps:

[0134] The pure sample of selenium gallium mercury magnesium powder obtained in Example 2 was mixed with element I and placed in a 25mm × 240mm quartz tube, and the mixture was evacuated to 100°C. -5 Pa was encapsulated in an oxyhydrogen flame and placed in a tube furnace for chemical vapor transport at a high temperature zone of 970°C and a low temperature zone of 820°C. MgHgGa4Se8 crystals were grown through a vertical gradient temperature field. The temperature was simultaneously increased to 970°C in the high temperature zone and 820°C in the low temperature zone at a rate of 18°C / h, with a growth cycle of 18 days. After growth, the temperature was slowly reduced to room temperature at a rate of 3°C / h, the tube furnace was shut off, and the quartz tube was cut after cooling. A Φ5×3mm red selenium gallium mercury magnesium infrared nonlinear optical crystal was obtained at the low temperature end.

[0135] Example 27

[0136] The chemical vapor transport method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is performed according to the following steps:

[0137] The pure sample of selenium gallium mercury magnesium powder obtained in Example 3 was mixed with element I and placed into a 25mm × 240mm quartz tube, and the mixture was evacuated to 100°C. -5 Pa was encapsulated in an oxyhydrogen flame and placed in a tube furnace for chemical vapor transport at a high temperature zone of 990°C and a low temperature zone of 840°C. MgHgGa4Se8 crystals were grown through a vertical gradient temperature field. The temperature was simultaneously increased to 990°C in the high temperature zone and 840°C in the low temperature zone at a rate of 20°C / h for a growth period of 20 days. After growth, the temperature was slowly reduced to room temperature at a rate of 4°C / h, the tube furnace was shut off, and the quartz tube was cut after cooling. A Φ5.5×3mm red selenium gallium mercury magnesium infrared nonlinear optical crystal was obtained at the low temperature end.

[0138] Example 28

[0139] The chemical vapor transport method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is performed according to the following steps:

[0140] The pure sample of selenium gallium mercury magnesium powder obtained in Example 4 was mixed with element I and placed into a 25mm × 240mm quartz tube, and the tube was evacuated to 10°C. -5 The sample was encapsulated in an oxyhydrogen flame and placed in a tube furnace for chemical vapor transport at a high temperature of 1010°C and a low temperature of 860°C. MgHgGa4Se8 crystals were grown using a horizontal gradient temperature field. The temperature was simultaneously increased to 1010°C in the high temperature zone and 860°C in the low temperature zone at a rate of 22°C / h. The growth period was 23 days. After growth, the temperature was slowly reduced to room temperature at a rate of 5°C / h, the tube furnace was shut off, and the quartz tube was cut after cooling. A Φ5.5×3.5mm red selenium gallium mercury magnesium infrared nonlinear optical crystal was obtained at the low temperature end.

[0141] Example 29

[0142] The chemical vapor transport method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is performed according to the following steps:

[0143] The pure sample of selenium gallium mercury magnesium powder obtained in Example 5 was mixed with element I and placed in a 25mm × 240mm quartz tube, and the tube was evacuated to 100°C. -5Pa was encapsulated in an oxyhydrogen flame and placed in a tube furnace for chemical vapor transport at a high temperature zone of 1030°C and a low temperature zone of 880°C. MgHgGa4Se8 crystals were grown through a vertical gradient temperature field. The temperature was simultaneously increased to 1030°C in the high temperature zone and 880°C in the low temperature zone at a rate of 25°C / h. The growth cycle was 25 days. After the growth was completed, the temperature was slowly reduced to room temperature at a rate of 6°C / h. The tube furnace was then shut off, and the quartz tube was cut after cooling. A Φ5×4mm red selenium gallium mercury magnesium infrared nonlinear optical crystal was obtained at the low temperature end.

[0144] Example 30

[0145] The chemical vapor transport method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is performed according to the following steps:

[0146] The pure sample of selenium gallium mercury magnesium powder obtained in Example 6 was mixed with element I and placed in a 25mm × 240mm quartz tube, and the tube was evacuated to 100°C. -5 Pa was encapsulated in an oxyhydrogen flame and placed in a tube furnace for chemical vapor transport at a high temperature zone of 1030°C and a low temperature zone of 880°C. MgHgGa4Se8 crystals were grown through a horizontal gradient temperature field. The temperature was simultaneously increased to 1030°C in the high temperature zone and 880°C in the low temperature zone at a rate of 25°C / h. The growth cycle was 25 days. After the growth was completed, the temperature was slowly reduced to room temperature at a rate of 6°C / h. The tube furnace was then shut off, and the quartz tube was cut after cooling. A Φ5.5×4mm red selenium gallium mercury magnesium infrared nonlinear optical crystal was obtained at the low temperature end.

[0147] Example 31

[0148] The chemical vapor transport method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is performed according to the following steps:

[0149] The pure sample of selenium gallium mercury magnesium powder obtained in Example 7 was mixed with element I and placed in a 25mm × 240mm quartz tube, and the mixture was evacuated to 100°C. -5 Pa was encapsulated in an oxyhydrogen flame and placed in a tube furnace for chemical vapor transport at a high temperature zone of 1050°C and a low temperature zone of 900°C. MgHgGa4Se8 crystals were grown through a horizontal gradient temperature field. The temperature was simultaneously increased to 1050°C in the high temperature zone and 900°C in the low temperature zone at a rate of 25°C / h. The growth cycle was 28 days. After the growth was completed, the temperature was slowly reduced to room temperature at a rate of 7°C / h. The tube furnace was then shut off, and the quartz tube was cut after cooling. A Φ6×4mm red selenium gallium mercury magnesium infrared nonlinear optical crystal was obtained at the low temperature end.

[0150] Example 32

[0151] The chemical vapor transport method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is performed according to the following steps:

[0152] The pure sample of selenium gallium mercury magnesium powder obtained in Example 8 was mixed with element I and placed in a 25mm × 240mm quartz tube, and the tube was evacuated to 100°C. -5 Pa was encapsulated in an oxyhydrogen flame and placed in a tube furnace for chemical vapor transport at a high temperature of 1070°C and a low temperature of 900°C. MgHgGa4Se8 crystals were grown using a horizontal gradient temperature field. The temperature was simultaneously increased to 1050°C in the high temperature zone and 900°C in the low temperature zone at a rate of 25°C / h. The growth period was 30 days. After growth, the temperature was slowly reduced to room temperature at a rate of 8°C / h, the tube furnace was shut off, and the quartz tube was cut after cooling. A Φ6×4mm red selenium gallium mercury magnesium infrared nonlinear optical crystal was obtained at the low temperature end.

[0153] Example 33

[0154] The chemical vapor transport method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is performed according to the following steps:

[0155] The pure sample of selenium gallium mercury magnesium powder obtained in Example 9 was mixed with element I and placed into a 25mm × 240mm quartz tube, and the tube was evacuated to 100°C. -5 The sample was encapsulated in an oxyhydrogen flame and placed in a tube furnace for chemical vapor transport at a high temperature of 1090°C and a low temperature of 900°C. MgHgGa4Se8 crystals were grown using a horizontal gradient temperature field. The temperature was simultaneously increased to 1090°C in the high temperature zone and 900°C in the low temperature zone at a rate of 25°C / h. The growth period was 32 days. After growth, the temperature was slowly reduced to room temperature at a rate of 9°C / h, the tube furnace was shut off, and the quartz tube was cut after cooling. A Φ7×4mm red selenium gallium mercury magnesium infrared nonlinear optical crystal was obtained at the low temperature end.

[0156] Example 34

[0157] The chemical vapor transport method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is performed according to the following steps:

[0158] The pure sample of selenium gallium mercury magnesium powder obtained in Example 10 was mixed with element I and placed in a 25mm × 240mm quartz tube, and the tube was evacuated to 10°C. -5 Pa was encapsulated in an oxyhydrogen flame and placed in a tube furnace for chemical vapor transport at a high temperature zone of 1100°C and a low temperature zone of 900°C. MgHgGa4Se8 crystals were grown through a vertical gradient temperature field. The temperature was simultaneously increased to 1100°C in the high temperature zone and 900°C in the low temperature zone at a rate of 25°C / h. The growth cycle was 35 days. After the growth was completed, the temperature was slowly reduced to room temperature at a rate of 9°C / h. The tube furnace was then shut off, and the quartz tube was cut after cooling. A Φ7×5mm red selenium gallium mercury magnesium infrared nonlinear optical crystal was obtained at the low temperature end.

[0159] Example 35

[0160] The chemical vapor transport method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is performed according to the following steps:

[0161] The pure sample of selenium gallium mercury magnesium powder obtained in Example 11 was mixed with element I and placed in a 25mm × 240mm quartz tube, and the tube was evacuated to 10°C. -5 Pa was encapsulated in an oxyhydrogen flame and placed in a tube furnace for chemical vapor transport at a high temperature zone of 1050°C and a low temperature zone of 900°C. MgHgGa4Se8 crystals were grown through a vertical gradient temperature field. The temperature was simultaneously increased to 1050°C in the high temperature zone and 900°C in the low temperature zone at a rate of 20°C / h. The growth period was 35 days. After growth, the temperature was slowly reduced to room temperature at a rate of 6°C / h, the tube furnace was shut off, and the quartz tube was cut after cooling. A Φ7.5×5mm red selenium gallium mercury magnesium infrared nonlinear optical crystal was obtained at the low temperature end.

[0162] Example 36

[0163] The chemical vapor transport method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is performed according to the following steps:

[0164] The pure sample of selenium gallium mercury magnesium powder obtained in Example 12 was mixed with element I and placed in a 25mm × 240mm quartz tube, and the tube was evacuated to 10°C. -5 Pa was encapsulated in an oxyhydrogen flame and placed in a tube furnace for chemical vapor transport at a high temperature zone of 1000℃ and a low temperature zone of 850℃. MgHgGa4Se8 crystals were grown through a horizontal gradient temperature field. The temperature was simultaneously increased to 1000℃ in the high temperature zone and 850℃ in the low temperature zone at a rate of 15℃ / h. The growth cycle was 35 days. After the growth was completed, the temperature was slowly reduced to room temperature at a rate of 6℃ / h. The tube furnace was then shut off, and the quartz tube was cut after cooling. A Φ7×5mm red selenium gallium mercury magnesium infrared nonlinear optical crystal was obtained at the low temperature end.

[0165] Example 37

[0166] The crucible lowering method for growing selenium-gallium-mercury-magnesium infrared nonlinear optical crystals is performed according to the following steps:

[0167] The pure sample of selenium gallium mercury magnesium powder obtained in Example 1 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5After Pa, the material was encapsulated with an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature was increased to 950℃ at 5℃ / h and held at that temperature for 90h until the raw material was completely melted. Then, the crucible lowering furnace was lowered vertically at a speed of 1mm / h. During the descent, MgHgGa4Se8 crystals were grown for 15 days. After the crystal growth was completed, the crystal was left in the crucible lowering furnace for annealing and then cooled to room temperature at a rate of 40℃ / h to obtain a Φ6×3mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0168] Example 38

[0169] The crucible lowering method for growing selenium-gallium-mercury-magnesium infrared nonlinear optical crystals is performed according to the following steps:

[0170] The pure sample of selenium gallium mercury magnesium powder obtained in Example 2 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 After Pa, the material was encapsulated with an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature was increased to 960℃ at 8℃ / h and held at that temperature for 85h until the raw material was completely melted. Then, the crucible lowering furnace was lowered vertically at a speed of 1.2mm / h. During the descent, MgHgGa4Se8 crystals were grown for 18 days. After the crystal growth was completed, the crystal was left in the crucible lowering furnace for annealing and then cooled to room temperature at a rate of 36℃ / h to obtain a Φ6.5×2.5mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0171] Example 39

[0172] The crucible lowering method for growing selenium-gallium-mercury-magnesium infrared nonlinear optical crystals is performed according to the following steps:

[0173] The pure sample of selenium gallium mercury magnesium powder obtained in Example 3 was placed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 After Pa, the material is encapsulated with an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature is increased to 960℃ at 10℃ / h and held at that temperature for 80h until the raw material is completely melted. Then, the crucible lowering furnace is lowered vertically at a speed of 1.5mm / h. During the descent, MgHgGa4Se8 crystals are grown for 20 days. After the crystal growth is completed, the crystal is left in the crucible lowering furnace for annealing and then cooled to room temperature at a rate of 34℃ / h to obtain a Φ5×2.5mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0174] Example 40

[0175] The crucible lowering method for growing selenium-gallium-mercury-magnesium infrared nonlinear optical crystals is performed according to the following steps:

[0176] The pure sample of selenium gallium mercury magnesium powder obtained in Example 4 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 After Pa, the material was encapsulated with an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature was increased to 970℃ at 12℃ / h and held at that temperature for 75h until the raw material was completely melted. Then, the crucible lowering furnace was lowered vertically at a speed of 1.8mm / h. During the descent, MgHgGa4Se8 crystals were grown for 20 days. After the crystal growth was completed, the crystal was left in the crucible lowering furnace for annealing and then cooled to room temperature at a rate of 32℃ / h to obtain a Φ5×3mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0177] Example 41

[0178] The crucible lowering method for growing selenium-gallium-mercury-magnesium infrared nonlinear optical crystals is performed according to the following steps:

[0179] The pure sample of selenium gallium mercury magnesium powder obtained in Example 5 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 After Pa, the material was encapsulated with an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature was increased to 980℃ at 15℃ / h and held at that temperature for 75h until the raw material was completely melted. Then, the crucible lowering furnace was lowered vertically at a speed of 2mm / h. During the descent, MgHgGa4Se8 crystals were grown for 25 days. After the crystal growth was completed, the crystal was left in the crucible lowering furnace for annealing and then cooled to room temperature at a rate of 30℃ / h to obtain a Φ5.5×3mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0180] Example 42

[0181] The crucible lowering method for growing selenium-gallium-mercury-magnesium infrared nonlinear optical crystals is performed according to the following steps:

[0182] The pure sample of selenium gallium mercury magnesium powder obtained in Example 6 was placed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 After Pa, the material was encapsulated with an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature was increased to 980℃ at 17℃ / h and held at that temperature for 70h until the raw material was completely melted. Then, the crucible lowering furnace was lowered vertically at a speed of 2.2mm / h. During the descent, MgHgGa4Se8 crystals were grown, with a growth cycle of 25 days. After the crystal growth was completed, the crystal was left in the crucible lowering furnace for annealing and then cooled to room temperature at a rate of 28℃ / h to obtain a Φ5×2.5mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0183] Example 43

[0184] The crucible lowering method for growing selenium-gallium-mercury-magnesium infrared nonlinear optical crystals is performed according to the following steps:

[0185] The pure sample of selenium gallium mercury magnesium powder obtained in Example 7 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 After Pa, the material was encapsulated with an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature was increased to 990℃ at 20℃ / h and held at that temperature for 68h until the raw material was completely melted. Then, the crucible lowering furnace was lowered vertically at a speed of 2.5mm / h. During the descent, MgHgGa4Se8 crystals were grown for 25 days. After the crystal growth was completed, the crystal was left in the crucible lowering furnace for annealing and then cooled to room temperature at a rate of 25℃ / h to obtain a Φ4×2.5mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0186] Example 44

[0187] The crucible lowering method for growing selenium-gallium-mercury-magnesium infrared nonlinear optical crystals is performed according to the following steps:

[0188] The pure sample of selenium gallium mercury magnesium powder obtained in Example 8 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 After Pa, the material was encapsulated with an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature was increased to 1000℃ at 20℃ / h and held at that temperature for 60h until the raw material was completely melted. Then, the crucible lowering furnace was lowered vertically at a speed of 2.8mm / h. During the descent, MgHgGa4Se8 crystals were grown for 20 days. After the crystal growth was completed, the crystal was left in the crucible lowering furnace for annealing and then cooled to room temperature at a rate of 25℃ / h to obtain a Φ3×2.5mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0189] Example 45

[0190] The crucible lowering method for growing selenium-gallium-mercury-magnesium infrared nonlinear optical crystals is performed according to the following steps:

[0191] The pure sample of selenium gallium mercury magnesium powder obtained in Example 9 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 After Pa, the material was encapsulated with an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature was increased to 980℃ at 20℃ / h and held at that temperature for 65h until the raw material was completely melted. Then, the crucible lowering furnace was lowered vertically at a speed of 3mm / h. During the descent, MgHgGa4Se8 crystals were grown, with a growth cycle of 15 days. After the crystal growth was completed, the crystal was left in the crucible lowering furnace for annealing and then cooled to room temperature at a rate of 20℃ / h to obtain a Φ3×2mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0192] Example 46

[0193] The crucible lowering method for growing selenium-gallium-mercury-magnesium infrared nonlinear optical crystals is performed according to the following steps:

[0194] The pure sample of selenium gallium mercury magnesium powder obtained in Example 10 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 After Pa, the material was encapsulated with an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature was increased to 980℃ at 20℃ / h and held at that temperature for 80h until the raw material was completely melted. Then, the crucible lowering furnace was lowered vertically at a speed of 3mm / h. During the descent, MgHgGa4Se8 crystals were grown for 18 days. After the crystal growth was completed, the crystal was left in the crucible lowering furnace for annealing and then cooled to room temperature at a rate of 30℃ / h to obtain a Φ4×2.5mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0195] Example 47

[0196] The crucible lowering method for growing selenium-gallium-mercury-magnesium infrared nonlinear optical crystals is performed according to the following steps:

[0197] The pure sample of selenium gallium mercury magnesium powder obtained in Example 11 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 After Pa, the material was encapsulated with an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature was increased to 980℃ at 15℃ / h and held at that temperature for 70h until the raw material was completely melted. Then, the crucible lowering furnace was lowered vertically at a speed of 2mm / h. During the descent, MgHgGa4Se8 crystals were grown for 20 days. After the crystal growth was completed, the crystal was left in the crucible lowering furnace for annealing and then cooled to room temperature at a rate of 30℃ / h to obtain a Φ5×3mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0198] Example 48

[0199] The crucible lowering method for growing selenium-gallium-mercury-magnesium infrared nonlinear optical crystals is performed according to the following steps:

[0200] The pure sample of selenium gallium mercury magnesium powder obtained in Example 12 was packed into a 25mm × 240mm quartz tube and evacuated to 10°C. -5 After Pa, the material was encapsulated with an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature was increased to 980℃ at 15℃ / h and held at that temperature for 60h until the raw material was completely melted. Then, the crucible lowering furnace was lowered vertically at a speed of 1.5mm / h. During the descent, MgHgGa4Se8 crystals were grown for 20 days. After the crystal growth was completed, the crystal was left in the crucible lowering furnace for annealing and then cooled to room temperature at a rate of 40℃ / h to obtain a Φ6×2.5mm red selenium gallium mercury magnesium infrared nonlinear optical crystal.

[0201] Example 49

[0202] Any of the MgHgGa4Se8 infrared nonlinear optical crystals obtained in Examples 13-48 are placed... Figure 4 At position 3 of the device shown, at room temperature, a Q-switched Ho:Tm:Cr:YAG laser is used as the light source. The incident infrared light has a wavelength of 2090nm, and the output wavelength is 1045nm. The laser intensity output using MgHgGa4Se8 crystal is 1.8 times that of AgGaS2 under the same conditions.

[0203] Example 50

[0204] Any of the MgHgGa4Se8 infrared nonlinear optical crystals obtained in Examples 13-48, according to... Figure 4 As shown, the components are arranged at position 3, where 1 is a laser, 2 is a convex lens, 3 is a MgHgGa4Se8 infrared nonlinear optical crystal, 4 is a prism, and 5 is a filter. The laser beam emitted by the laser 1 passes through the convex lens 2 and enters the MgHgGa4Se8 crystal 3. The resulting outgoing laser beam passes through the prism 4 and the filter 5 to obtain the desired laser beam.

[0205] Devices made using the MgHgGa4Se8 infrared nonlinear optical crystal of this invention can be frequency multipliers, up-to-down frequency converters, optical parametric oscillators, and optical parametric amplifiers.

[0206] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to the embodiments, those skilled in the art should understand that modifications or equivalent substitutions to the technical solutions of the present invention do not depart from the spirit and scope of the present invention.

Claims

1. A compound, selenium gallium mercury magnesium, characterized in that... The compound has the molecular formula MgHgGa4Se8, a molecular weight of 1135.46 g / mol, belongs to the tetragonal crystal system, and crystallizes in the non-central space group. It is produced by high-temperature solid-state method.

2. The method for preparing the compound selenium gallium mercury magnesium according to claim 1, characterized in that... The compound has the molecular formula MgHgGa4Se8 and was prepared using a high-temperature solid-state method. The specific steps are as follows: a. Using a molar ratio of Mg:Hg:Ga:Se = 1:1:4:8, mix Mg or MgSe (Mg source material), Hg or HgSe (Hg source material), and Ga, GaSe or Ga2Se3 (Ga source material) with elemental Se until homogeneous. Grind the mixture and place it into a 25mm × 240mm quartz container. Evacuate the container to 100°C. -3 -10 -5 Pa and perform melt sealing; b. Place the sealed sample from step a in a muffle furnace and heat it to 800-920℃ at a rate of 10-40℃ / h. Hold the temperature for 60-80 hours, then reduce the temperature to 400℃ at a rate of 10-20℃ / h. Allow it to cool naturally to room temperature. After cooling, remove the sample and crush and grind it to obtain powdered MgHgGa4Se8 compound.

3. A selenium-gallium-mercury-magnesium infrared nonlinear optical crystal, characterized in that, The crystal has the molecular formula MgHgGa4Se8, a molecular weight of 1135.46 g / mol, lacks a center of symmetry, belongs to the tetragonal crystal system, and has a space group of [space group number missing]. Cell parameters are α=β=γ=90°, Z=1.

4. The method for preparing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal according to claim 3, characterized in that... Crystal growth can be performed using the high-temperature melt method, chemical vapor transport method, or crucible descent method. The high-temperature melt method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is carried out according to the following steps: a. Using a molar ratio of Mg:Hg:Ga:Se = 1:1:4:8, mix Mg or MgSe as the Mg source material; Hg or HgSe as the Hg source material; and Ga, GaSe, or Ga2Se3 as the Ga source material with elemental Se until homogeneous. Then, pack the mixture into a 25mm × 240mm quartz tube and evacuate to 100°C. -3 -10 -5 Pa was sealed and placed in a muffle furnace. The temperature was increased to 800-920℃ at a rate of 10-40℃ / h and held at that temperature for 60-80h. The temperature was then reduced to 400℃ at a rate of 10-20℃ / h. After cooling to room temperature naturally, the sample was removed, crushed, and ground to obtain a powdered pure MgHgGa4Se8 sample. b. Place the obtained pure sample powder into a quartz tube and evacuate to 10°C. -3 -10 -5 Pa was encapsulated in an oxyhydrogen flame, placed in a muffle furnace, and slowly heated to 930-1000℃, held at that temperature for 48-72 hours, then slowly cooled to 800℃ at a rate of 1-5℃ / h, and then cooled to room temperature at a rate of 10-20℃ / h. The muffle furnace was then turned off, and the quartz tube was cut open after cooling to obtain a red MgHgGa4Se8 infrared nonlinear optical crystal. The chemical vapor transport method for growing the selenium-gallium-mercury-magnesium infrared nonlinear optical crystal is performed according to the following steps: a. Using a molar ratio of Mg:Hg:Ga:Se = 1:1:4:8, mix Mg or MgSe as the Mg source material; Hg or HgSe as the Hg source material; and Ga, GaSe, or Ga2Se3 as the Ga source material with elemental Se until homogeneous. Then, pack the mixture into a 25mm × 240mm quartz tube and evacuate to 100°C. -3 -10 -5 Pa was encapsulated in an oxyhydrogen flame, placed in a muffle furnace, heated to 800-920℃ at a rate of 10-40℃ / h, held at the temperature for 60-80h, and then cooled to 400℃ at a rate of 10-20℃ / h. After that, the sample was naturally cooled to room temperature, removed, and crushed and ground to obtain a pure powder of MgHgGa4Se8. b. The pure sample powder obtained in step a is mixed with elemental I2 and chemically transported in a tube furnace. The high temperature zone is 950-1100℃ and the low temperature zone is 800-900℃. MgHgGa4Se8 crystals are grown through a horizontal or vertical gradient temperature field. The temperature is simultaneously raised to 950-1100℃ in the high temperature zone and 800-900℃ in the low temperature zone at a rate of 15-25℃ / h. The growth cycle is 15-35 days. After the growth is completed, the temperature is slowly lowered to room temperature at a rate of 2-9℃ / h. The tube furnace is then turned off. After the quartz tube cools down, it is cut open to obtain a red MgHgGa4Se8 infrared nonlinear optical crystal at the low temperature end. The crucible lowering method for growing selenium-gallium-mercury-magnesium infrared nonlinear optical crystals is performed according to the following steps: a. Using a molar ratio of Mg:Hg:Ga:Se = 1:1:4:8, mix Mg or MgSe as the Mg source material; Hg or HgSe as the Hg source material; and Ga, GaSe, or Ga2Se3 as the Ga source material with elemental Se until homogeneous. Then, pack the mixture into a 25mm × 240mm quartz tube and evacuate to 100°C. -3 -10 -5 Pa was encapsulated in an oxyhydrogen flame, placed in a muffle furnace, heated to 800-920℃ at a rate of 10-40℃ / h, held at the temperature for 60-80h, and then cooled to 400℃ at a rate of 10-20℃ / h. After that, the sample was naturally cooled to room temperature, removed, and crushed and ground to obtain a pure powder of MgHgGa4Se8. b. Place the obtained pure sample powder into a quartz tube and evacuate to 10°C. -3 -10 -5 Pa is encapsulated in an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature is increased to 940-1000℃ at a rate of 5-20℃ / h and held at that temperature for 60-100h until the raw material is completely melted. The crucible lowering furnace is then lowered vertically at a rate of 1-3mm / h, during which crystal growth takes place. The growth cycle is 15-25 days. After the crystal growth is completed, the crystal is left in the crucible lowering furnace for annealing and then cooled to room temperature at a rate of 20-40℃ / h to obtain a red MgHgGa4Se8 infrared nonlinear optical crystal.

5. The use of the selenium gallium mercury magnesium infrared nonlinear optical crystal as described in claim 3 in the preparation of infrared band laser frequency conversion crystals, infrared all-solid-state lasers, infrared electro-optic devices, infrared communication devices, or infrared laser guidance devices.

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