Selenium-gallium-mercury-magnesium compound, selenium-gallium-mercury-magnesium infrared nonlinear optical crystal, preparation method and application

Abstract

The invention relates to a selenium-gallium-mercury-magnesium compound and a selenium-gallium-mercury-magnesium infrared nonlinear optical crystal as well as a preparation method and application thereof, the molecular formula of the compound is MgHgGa4Se8, the molecular weight of the compound is 1135.46 g / mol, the molecular formula of the crystal is MgHgGa4Se8, the molecular weight of the crystal is 1135.46 g / mol, the crystal has no symmetry center and belongs to a tetragonal crystal system, the space group is # imgabs0 #, the cell parameters are as follows: # imgabs1 # and # imgabs2 #, alpha = beta = gamma = 90 degrees, Z = 1, and beta = gamma = 90 degrees. And the crystal is prepared by adopting a high-temperature melt method, a chemical vapor transport method or a Bridgman-Stockbarger method, wherein the volume of the crystal is # imgabs3 # and # imgabs4 #. The crystal has the advantages of being large in nonlinear optical effect, good in crystal growth habit, good in mechanical performance, large in hardness, not prone to fragmentation and deliquescence, easy to process and store and the like, can be used for manufacturing infrared nonlinear optical devices, and has important application in the fields of photoelectric countermeasure, laser communication, medical treatment and the like.

Description

Technical Field

[0001] The present invention belongs to the field of preparation of infrared nonlinear optical crystals, and particularly relates to a magnesium mercury gallium selenium (MgHgGa 4 Se 8 ) compound, a magnesium mercury gallium selenium infrared nonlinear optical crystal, a preparation method and an application thereof. Background Art

[0002] Nonlinear optical crystals are a kind of crystal materials with nonlinear optical effects such as frequency doubling, sum frequency, difference frequency, optical parametric amplification, etc. Only crystals with an asymmetric center can produce second-order nonlinear optical effects. By utilizing the second-order nonlinear optical effects of crystals, nonlinear optical devices such as second harmonic generators, up and down frequency converters, optical parametric oscillators, etc. 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. 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. Among them, the nonlinear optical crystal materials in the ultraviolet, visible and near-infrared light regions can basically meet the requirements of practical applications. For example, in the frequency doubling (532 nm) crystals, the mainly practical ones are KTP (KTiOPO 4 ), β-BBO (β-BaB 2 O 4 ), LBO (LiB 3 O 5 ) crystals; in the deep ultraviolet crystals, the practical ones are KBBF (KBe 2 BO 3 F 2 ), ABF (NH 4 B 4 O 6 F) for selection. 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, narrow band gap, two-photon absorption near 1 μm, etc., the application of these materials in the current high-power laser output field has been greatly limited and can no longer fully meet the application 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

[0003] The object of the present invention is to provide a compound with the chemical formula MgHgGa 4 Se8 The compound magnesium mercury gallium selenide, with a molecular weight of 1135.46 g / mol, is prepared by the high-temperature solid-state method.

[0004] Another object of the present invention is to provide MgHgGa 4 Se 8 an infrared nonlinear optical crystal, the crystal formula of which is MgHgGa 4 Se 8 , with a molecular weight of 1135.46 g / mol, having no center of symmetry, belonging to the tetragonal crystal system, and the space group is The unit cell parameters are: α = β = γ = 90°, Z = 1, and the volume is

[0005] Another object of the present invention is to provide MgHgGa 4 Se 8 a preparation method of a nonlinear optical crystal.

[0006] Another object of the present invention is to provide MgHgGa 4 Se 8 the use of a nonlinear optical crystal.

[0007] A compound magnesium mercury gallium selenide according to the present invention, the chemical formula of the compound is MgHgGa 4 Se 8 , with a molecular weight of 1135.46 g / mol, belonging to the tetragonal crystal system, crystallizing in a non-centrosymmetric space group of and is prepared by the high-temperature solid-state method.

[0008] The preparation method of the said compound magnesium mercury gallium selenide, the chemical formula of the compound is MgHgGa 4 Se 8 , is prepared by the high-temperature solid-state method, and the specific operation is carried out according to the following steps:

[0009] a. Mix the Mg source material, which is Mg or MgSe; the Hg source material, which is Hg or HgSe; the Ga source material, which is Ga, GaSe or Ga 2 Se 3 with elemental Se evenly, grind, load into a quartz container with a diameter of Φ25 mm × 240 mm, evacuate to 10 -3 -10 -5 Pa and perform melting and sealing;

[0010] b. Place the sealed sample from step a in a muffle furnace, heat it at a rate of 10 - 40 °C / h to 800 - 920 °C, keep it at a constant temperature for 60 - 80 hours, cool it to 400 °C at a rate of 10 - 20 °C / h, and then let it cool naturally to room temperature. After cooling, take out the sample and crush and grind it to obtain powdered MgHgGa 4 Se 8 compound.

[0011] A mercury magnesium gallium selenide infrared nonlinear optical crystal, the crystal formula of which is MgHgGa 4 Se 8 , with a molecular weight of 1135.46 g / mol, having no center of symmetry, belonging to the tetragonal crystal system, and the space group is The unit cell parameters are α = β = γ = 90°, Z = 1.

[0012] The preparation method of the mercury magnesium gallium selenide infrared nonlinear optical crystal adopts the high-temperature melt method, chemical vapor transport method or Bridgman method for crystal growth:

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

[0014] a. Mix the Mg source material (Mg or MgSe), Hg source material (Hg or HgSe), Ga source material (Ga, GaSe or Ga 2 Se 3 with elemental Se evenly, load it into a quartz tube with a diameter of Φ25mm × 240mm, evacuate to 10 -3 -10 -5 Pa and seal it, place it in a muffle furnace, heat it at a rate of 10 - 40 °C / h to 800 - 920 °C, keep it at a constant temperature for 60 - 80 h, cool it to 400 °C at a rate of 10 - 20 °C / h, and then let it cool naturally to room temperature. After taking out the sample, crush and grind it to obtain powdered MgHgGa 4 Se 8 pure sample;

[0015] b. Load the obtained pure sample powder into a quartz tube, evacuate to 10 -3 -10 -5 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, slowly heat it to 930 - 1000 °C, keep it at a constant temperature for 48 - 72 h, then slowly cool it to 800 °C at a rate of 1 - 5 °C / h, and then cool it to room temperature at a rate of 10 - 20 °C / h. Turn off the muffle furnace. After the quartz tube cools, cut it open to obtain a red MgHgGa 4 Se 8 infrared nonlinear optical crystal;

[0016] The growth of mercury magnesium gallium selenide infrared nonlinear optical crystal by chemical vapor transport method is carried out according to the following steps:

[0017] a. Mix the Mg source material (Mg or MgSe), Hg source material (Hg or HgSe), Ga source material (Ga, GaSe or Ga 2 Se 3 with elemental Se evenly, then load them into a quartz tube with a size of Φ25mm×240mm, evacuate to 10 -3 -10 -5 Pa, seal it with a hydrogen-oxygen flame, put it into a muffle furnace, heat it up to 800-920°C at a rate of 10-40°C / h, keep it at a constant temperature for 60-80h, cool it down to 400°C at a rate of 10-20°C / h, then naturally cool it to room temperature, take out the sample, and crush and grind it to obtain powdery MgHgGa 4 Se 8 pure sample;

[0018] b. Carry out chemical vapor transport of the obtained pure sample powder and I element in a tube growth furnace. The high-temperature zone is 950-1100°C and the low-temperature zone is 800-900°C. The crystal growth of MgHgGa 4 Se 8 is carried out through a horizontal or vertical gradient temperature field. Heat up to 950-1100°C in the high-temperature zone and 800-900°C in the low-temperature zone at a rate of 15-25°C / h simultaneously. The growth period is 15-35 days. After the growth is completed, slowly cool it down to room temperature at a rate of 2-9°C / h, turn off the tube growth furnace, cut it open after the quartz tube cools down, and obtain a red MgHgGa 4 Se 8 infrared nonlinear optical crystal at the low-temperature end;

[0019] The growth of mercury magnesium gallium selenide infrared nonlinear optical crystal by the Bridgman method is carried out according to the following steps:

[0020] a. Mix the Mg source material (Mg or MgSe), Hg source material (Hg or HgSe), Ga source material (Ga, GaSe or Ga 2 Se 3 with elemental Se evenly, then load them into a quartz tube with a size of Φ25mm×240mm, evacuate to 10 -3 -10 -5 Pa, seal it with a hydrogen-oxygen flame, put it into a muffle furnace, heat it up to 800-920°C at a rate of 10-40°C / h, keep it at a constant temperature for 60-80h, cool it down to 400°C at a rate of 10-20°C / h, then naturally cool it to room temperature, take out the sample, and crush and grind it4 Se 8 Pure sample;

[0021] b. Load the obtained pure sample powder into a quartz tube, evacuate to 10 -3 -10 -5 Pa, seal with a hydrogen-oxygen flame, place in a crucible lowering furnace, heat to 940 - 1000 °C at a rate of 5 - 20 °C / h, keep at a constant temperature for 60 - 100 h until the raw materials are completely melted, then lower the crucible lowering furnace vertically at a speed of 1 - 3 mm / h, and conduct crystal growth during the lowering process. The growth period is 15 - 25 days. After the crystal growth is completed, leave the crystal in the crucible lowering furnace for annealing, cool to room temperature at a rate of 20 - 40 °C / h to obtain a red MgHgGa 4 Se 8 Infrared nonlinear optical crystal.

[0022] Use of the magnesium mercury gallium selenide infrared nonlinear optical crystal in preparing an infrared band laser frequency conversion crystal, an infrared all-solid-state laser, an infrared electro-optic device, an infrared communication device or an infrared laser guidance device.

[0023] The preparation method of the magnesium mercury gallium selenide infrared nonlinear optical crystal described in the present invention can obtain MgHgGa with a centimeter-scale size 4 Se 8 Nonlinear optical crystal; by using a large-sized crucible and extending the growth time, a correspondingly larger-sized MgHgGa 4 Se 8 Nonlinear optical crystal can be obtained.

[0024] The magnesium mercury gallium selenide infrared nonlinear optical crystal described in the present invention has the advantages of relatively low synthesis temperature, no inclusions, low cost, and easy access to relatively large-sized crystals; the obtained magnesium mercury gallium selenide infrared nonlinear optical crystal and device have the advantages of anti-laser damage, large nonlinear optical effect, wide light transmission band, high hardness, good mechanical properties, not easy to break and deliquesce, easy to process and preserve, etc.; the MgHgGa 4 Se 8 Nonlinear optical crystal can be used to fabricate infrared nonlinear optical devices.

[0025] According to the crystallographic data of the crystal, orient the crystal blank, cut the crystal at the required angles, thicknesses and cross-sectional dimensions, and polish the light-transmitting surface of the crystal, then it can be used as a nonlinear optical device.

[0026] The application of the magnesium mercury gallium selenide infrared nonlinear optical crystal described in the present invention in the field of laser technology includes uses in preparing an infrared band laser frequency conversion crystal, an infrared laser, an infrared electro-optic device, an infrared communication device or an infrared laser guidance device.

[0027] A compound MgHgGa according to the present invention 4 Se 8 can be prepared according to the following chemical reaction formulas:

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

[0029] (2) Mg + Hg + 4GaSe + 4Se = MgHgGa 4 Se 8 ;

[0030] (3) Mg + Hg + 2Ga 2 Se 3 + 2Se = MgHgGa 4 Se 8 ;

[0031] (4) Mg + HgSe + 4Ga + 7Se = MgHgGa 4 Se 8 ;

[0032] (5) Mg + HgSe + 4GaSe + 3Se = MgHgGa 4 Se 8 ;

[0033] (6) Mg + HgSe + 2Ga 2 Se 3 + Se = MgHgGa 4 Se 8 ;

[0034] (7) MgSe + Hg + 4Ga + 7Se = MgHgGa 4 Se 8 ;

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

[0036] (9) MgSe + Hg + 2Ga 2 Se 3 + Se = MgHgGa 4 Se 8 ;

[0037] (10) MgSe + HgSe + 4Ga + 6Se = MgHgGa 4 Se 8 ;

[0038] (11) MgSe + HgSe + 4GaSe + 2Se = MgHgGa4 Se 8 ;

[0039] (12)MgSe + HgSe + 2Ga 2 Se 3 = MgHgGa 4 Se 8 . BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 FIG. is a schematic structural diagram of the magnesium mercury gallium selenide crystal of the present invention, in which magnesium / mercury atoms are tetracoordinated with selenium atoms to form [(MgHg)Se 4 unit, and gallium atoms are coordinated with selenium atoms to form [GaSe 4 ( Figure 1 a); Then, [(MgHg)Se 4 and [GaSe 4 units are interconnected through corner sharing and edge sharing to construct a diamond-like three-dimensional structure ( Figure 1 b-e);

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

[0042] Figure 3 FIG. is a schematic diagram of the second-order NLO effect signal of the crystal of the present invention. Magnesium mercury gallium selenide exhibits a phase-matched large NLO response, which is about 1.8 times that of the reference AgGaS 2 .

[0043] Figure 4 FIG. is a schematic working principle diagram of the optical device of the present invention, where 1 is a laser, 2 is a convex lens, 3 is MgHgGa 4 Se 8 nonlinear optical crystal after crystal post-treatment and optical processing, 4 is a prism, and 5 is a filter. DETAILED DESCRIPTION OF THE INVENTION

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

[0045] Example 1

[0046] Using the chemical reaction formula Mg + Hg + 4Ga + 8Se = MgHgGa 4 Se 8 , the compound MgHgGa 4 Se 8 is prepared by the high-temperature solid-phase method. The specific operation is carried out according to the following steps:

[0047] Mix 0.107 g of metallic element Mg, 0.883 g of metallic element Hg, 1.228 g of metallic element Ga and 2.782 g of elemental Se evenly, then put them into a quartz glass tube with Φ25mm×240mm, and use a vacuum pump to pump the quartz tube to a vacuum degree of 10 -3 -10 -5 Pa, and then carry out melting and sealing;

[0048] Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it to 800 °C at a rate of 40 °C / h, keep it at a constant temperature for 80 h, then cool it to 400 °C at a speed of 20 °C / h, and then naturally cool it to room temperature, take out the sample, and crush and grind it to obtain a powdery selenium gallium mercury magnesium compound.

[0049] Example 2

[0050] According to the chemical reaction formula Mg + Hg + 4GaSe + 4Se = MgHgGa 4 Se 8 , prepare the compound MgHgGa 4 Se 8 by the high-temperature solid-phase method, and the specific operation is carried out according to the following steps:

[0051] Mix 0.109 g of metallic element Mg, 0.896 g of metallic element Hg, 2.584 g of the compound GaSe and 1.411 g of elemental Se evenly, then put them into a quartz glass tube with Φ25mm×240mm, and use a vacuum pump to pump the quartz tube to a vacuum degree of 10 -3 -10 -5 Pa, and then carry out melting and sealing;

[0052] Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it to 820 °C at a rate of 36 °C / h, keep it at a constant temperature for 76 h, then cool it to 400 °C at a speed of 18 °C / h, and then naturally cool it to room temperature, take out the sample, and crush and grind it to obtain a powdery selenium gallium mercury magnesium compound.

[0053] Example 3

[0054] According to the chemical reaction formula Mg + Hg + 2Ga 2 Se 3 + 2Se = MgHgGa 4 Se 8 , prepare the compound MgHgGa 4 Se 8 by the high-temperature solid-phase method, and the specific operation is carried out according to the following steps:

[0055] Mix 0.107 g of metallic element Mg, 0.883 g of metallic element Hg, 3.314 g of the compound Ga 2 Se 3After being uniformly mixed with 0.695 g of elemental Se, it was placed into a quartz glass tube with a diameter of Φ25 mm and a length of 240 mm. The quartz tube was evacuated to a vacuum degree of 10 -3 -10 -5 Pa by a vacuum pump and then subjected to melting and sealing;

[0056] The sealed quartz tube was placed into a programmable temperature-controlled muffle furnace, heated to 840 °C at a rate of 32 °C / h, held at a constant temperature for 74 h, then cooled to 400 °C at a rate of 16 °C / h, and subsequently naturally cooled to room temperature. The sample was taken out, crushed and ground to obtain a powdery selenium gallium mercury magnesium compound.

[0057] Example 4

[0058] Based on the chemical reaction formula Mg + HgSe + 4Ga + 7Se = MgHgGa 4 Se 8 , the compound MgHgGa 4 Se 8 was prepared by the high-temperature solid-phase method. The specific operation was carried out according to the following steps:

[0059] After uniformly mixing 0.113 g of metallic elemental Mg, 1.010 g of the compound HgSe, 1.300 g of metallic elemental Ga, and 2.577 g of elemental Se, it was placed into a quartz glass tube with a diameter of Φ25 mm and a length of 240 mm. The quartz tube was evacuated to a vacuum degree of 10 -3 -10 -5 Pa by a vacuum pump and then subjected to melting and sealing;

[0060] The sealed quartz tube was placed into a programmable temperature-controlled muffle furnace, heated to 860 °C at a rate of 28 °C / h, held at a constant temperature for 72 h, then cooled to 400 °C at a rate of 14 °C / h, and subsequently naturally cooled to room temperature. The sample was taken out, crushed and ground to obtain a powdery selenium gallium mercury magnesium compound.

[0061] Example 5

[0062] Based on the chemical reaction formula Mg + HgSe + 4GaSe + 3Se = MgHgGa 4 Se 8 , the compound MgHgGa 4 Se 8 was prepared by the high-temperature solid-phase method. The specific operation was carried out according to the following steps:

[0063] After uniformly mixing 0.115 g of metallic elemental Mg, 1.025 g of the compound HgSe, 2.738 g of the compound GaSe, and 1.121 g of elemental Se, it was placed into a quartz glass tube with a diameter of Φ25 mm and a length of 240 mm. The quartz tube was evacuated to a vacuum degree of 10 -3 -10 -5 Pa by a vacuum pump and then subjected to melting and sealing;

[0064] Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it up to 880 °C at a rate of 24 °C / h, keep it at a constant temperature for 70 h, then cool it down to 400 °C at a rate of 12 °C / h, and then take out the sample after natural cooling to room temperature, and crush and grind it to obtain a powdery mercury magnesium gallium selenide compound.

[0065] Example 6

[0066] According to the chemical reaction formula Mg + HgSe + 4GaSe + 3Se = MgHgGa 4 Se 8 , prepare the compound MgHgGa 4 Se 8 by the high-temperature solid-phase method. The specific operation is carried out according to the following steps:

[0067] Mix 0.115 g of metallic element Mg, 1.025 g of the compound HgSe, 2.738 g of the compound GaSe and 1.121 g of elemental Se evenly, put them into a quartz glass tube with a diameter of Φ25 mm × 240 mm, and use a vacuum pump to pump the quartz tube to 10 -3 -10 -5 Pa vacuum and then carry out melting and sealing;

[0068] Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it up to 900 °C at a rate of 20 °C / h, keep it at a constant temperature for 68 h, then cool it down to 400 °C at a rate of 10 °C / h, and then take out the sample after natural cooling to room temperature, and crush and grind it to obtain a powdery mercury magnesium gallium selenide compound.

[0069] Example 7

[0070] According to the chemical reaction formula MgSe + Hg + 4Ga + 7Se = MgHgGa 4 Se 8 , prepare the compound MgHgGa 4 Se 8 by the high-temperature solid-phase method. The specific operation is carried out according to the following steps:

[0071] Mix 0.455 g of the compound Mg, 0.883 g of metallic element Hg, 1.228 g of metallic element Ga and 2.434 g of elemental Se evenly, put them into a quartz glass tube with a diameter of Φ25 mm × 240 mm, and use a vacuum pump to pump the quartz tube to 10 -3 -10 -5 Pa vacuum and then carry out melting and sealing;

[0072] Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it up to 900 °C at a rate of 18 °C / h, keep it at a constant temperature for 60 h, then cool it down to 400 °C at a rate of 10 °C / h, and then take out the sample after natural cooling to room temperature, and crush and grind it to obtain a powdery magnesium mercury gallium selenide compound.

[0073] Example 8

[0074] With the chemical reaction formula MgSe + Hg + 4GaSe + 3Se = MgHgGa 4 Se 8 , prepare the compound MgHgGa 4 Se 8 by the high-temperature solid-phase method, and the specific operation is carried out according to the following steps:

[0075] Mix 0.461 g of the compound MgSe, 0.896 g of the metal element Hg, 2.584 g of the compound GaSe and 1.058 g of the element Se evenly, put them into a quartz glass tube with a diameter of Φ25 mm × 240 mm, and use a vacuum pump to pump the quartz tube to 10 -3 -10 -5 Pa vacuum degree and then carry out melting and sealing;

[0076] Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it up to 920 °C at a rate of 18 °C / h, keep it at a constant temperature for 66 h, then cool it down to 400 °C at a rate of 10 °C / h, and then take out the sample after natural cooling to room temperature, and crush and grind it to obtain a powdery magnesium mercury gallium selenide compound.

[0077] Example 9

[0078] With the chemical reaction formula MgSe + Hg + 2Ga 2 Se 3 + Se = MgHgGa 4 Se 8 , prepare the compound MgHgGa 4 Se 8 by the high-temperature solid-phase method, and the specific operation is carried out according to the following steps:

[0079] Mix 0.455 g of the compound MgSe, 0.883 g of the metal element Hg, 3.314 g of the compound Ga 2 Se 3 and 0.348 g of the element Se evenly, put them into a quartz glass tube with a diameter of Φ25 mm × 240 mm, and use a vacuum pump to pump the quartz tube to 10 -3 -10 -5 Pa vacuum degree and then carry out melting and sealing;

[0080] Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it up to 920 °C at a rate of 12 °C / h, keep it at a constant temperature for 60 h, then cool it down to 400 °C at a rate of 16 °C / h, and then take out the sample after natural cooling to room temperature, and crush and grind it to obtain a powdery magnesium mercury gallium selenide compound.

[0081] Example 10

[0082] Using the chemical reaction formula MgSe + HgSe + 4Ga + 6Se = MgHgGa 4 Se 8 , prepare the compound MgHgGa 4 Se 8 by the high-temperature solid-phase method, and the specific operation is carried out according to the following steps:

[0083] Mix 0.481 g of the compound MgSe, 1.010 g of the compound HgSe, 1.300 g of the metal element Ga and 2.209 g of the element Se evenly, put them into a quartz glass tube with a diameter of Φ25 mm × 240 mm, and use a vacuum pump to pump the quartz tube to 10 -3 -10 -5 Pa vacuum degree and then carry out melting and sealing;

[0084] Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it up to 900 °C at a rate of 16 °C / h, keep it at a constant temperature for 60 h, then cool it down to 400 °C at a rate of 10 °C / h, and then take out the sample after natural cooling to room temperature, and crush and grind it to obtain a powdery magnesium mercury gallium selenide compound.

[0085] Example 11

[0086] Using the chemical reaction formula MgSe + HgSe + 4GaSe + 2Se = MgHgGa 4 Se 8 , prepare the compound MgHgGa 4 Se 8 by the high-temperature solid-phase method, and the specific operation is carried out according to the following steps:

[0087] Mix 0.489 g of the compound MgSe, 1.025 g of the compound HgSe, 2.738 g of the compound GaSe and 0.747 g of the element Se evenly, put them into a quartz glass tube with a diameter of Φ25 mm × 240 mm, and use a vacuum pump to pump the quartz tube to 10 -3 -10 -5 Pa vacuum degree and then carry out melting and sealing;

[0088] Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it to 900 °C at a rate of 20 °C / h, keep it at a constant temperature for 60 h, then cool it to 400 °C at a speed of 16 °C / h, and then take out the sample after natural cooling to room temperature, and crush and grind it to obtain a powdery magnesium mercury gallium selenide compound.

[0089] Example 12

[0090] According to the chemical reaction formula MgSe + HgSe + 2Ga 2 Se 3 = MgHgGa 4 Se 8 , prepare the compound MgHgGa 4 Se 8 by the high-temperature solid-phase method, and the specific operation is carried out according to the following steps:

[0091] Mix 0.481 grams of the compound MgSe, 1.010 grams of the compound HgSe and 3.509 grams of the compound Ga 2 Se 3 evenly, put it into a quartz glass tube with a diameter of Φ25mm × 240mm, and use a vacuum pump to pump the quartz tube to 10 -3 -10 -5 Pa vacuum degree and then carry out melting and sealing;

[0092] Put the sealed quartz tube into a programmable temperature-controlled muffle furnace, heat it to 900 °C at a rate of 16 °C / h, keep it at a constant temperature for 70 h, then cool it to 400 °C at a speed of 20 °C / h, and then take out the sample after natural cooling to room temperature, and crush and grind it to obtain a powdery magnesium mercury gallium selenide compound.

[0093] Example 13

[0094] For the growth of magnesium mercury gallium selenide infrared nonlinear optical crystal by the high-temperature melt method, the specific operation is carried out according to the following steps:

[0095] Put the pure sample of magnesium mercury gallium selenide powder obtained in Example 1 into a quartz tube with a diameter of Φ25mm × 240mm, evacuate it to 10 -5 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, slowly heat it to a temperature of 930 °C, keep it at a constant temperature for 72 h, then slowly cool it to 800 °C room temperature at a rate of 5 °C / h, and then cool it to room temperature at a rate of 20 °C / h, turn off the muffle furnace, and cut it after the quartz tube cools to obtain a Φ3 × 2 mm red magnesium mercury gallium selenide infrared nonlinear optical crystal.

[0096] Example 14

[0097] For the growth of magnesium mercury gallium selenide infrared nonlinear optical crystal by the high-temperature melt method, the specific operation is carried out according to the following steps:

[0098] Put the pure sample of selenium-gallium-mercury-magnesium powder obtained in Example 2 into a quartz tube with a diameter of Φ25mm×240mm, evacuate to 10 -5 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, slowly heat it to a temperature of 940 °C, keep it at a constant temperature for 70 h, then slowly cool it to 800 °C room temperature at a rate of 5 °C / h, and then cool it to room temperature at a rate of 18 °C / h. Turn off the muffle furnace. After the quartz tube cools, cut it open to obtain a Φ3×1mm red selenium-gallium-mercury-magnesium infrared nonlinear optical crystal.

[0099] Example 15

[0100] For the growth of selenium-gallium-mercury-magnesium infrared nonlinear optical crystals by the high-temperature melt method, the specific operation is carried out according to the following steps:

[0101] Put the pure sample of selenium-gallium-mercury-magnesium powder obtained in Example 3 into a quartz tube with a diameter of Φ25mm×240mm, evacuate to 10 -5 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, slowly heat it to a temperature of 950 °C, keep it at a constant temperature for 68 h, then slowly cool it to 800 °C room temperature at a rate of 5 °C / h, and then cool it to room temperature at a rate of 16 °C / h. Turn off the muffle furnace. After the quartz tube cools, cut it open to obtain a Φ3×3mm red selenium-gallium-mercury-magnesium infrared nonlinear optical crystal.

[0102] Example 16

[0103] For the growth of selenium-gallium-mercury-magnesium infrared nonlinear optical crystals by the high-temperature melt method, the specific operation is carried out according to the following steps:

[0104] Put the pure sample of selenium-gallium-mercury-magnesium powder obtained in Example 4 into a quartz tube with a diameter of Φ25mm×240mm, evacuate to 10 -5 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, slowly heat it to a temperature of 960 °C, keep it at a constant temperature for 66 h, then slowly cool it to 800 °C room temperature at a rate of 4 °C / h, and then cool it to room temperature at a rate of 16 °C / h. Turn off the muffle furnace. After the quartz tube cools, cut it open to obtain a Φ5×3mm red selenium-gallium-mercury-magnesium infrared nonlinear optical crystal.

[0105] Example 17

[0106] For the growth of selenium-gallium-mercury-magnesium infrared nonlinear optical crystals by the high-temperature melt method, the specific operation is carried out according to the following steps:

[0107] Put the pure sample of selenium-gallium-mercury-magnesium powder obtained in Example 5 into a quartz tube with a diameter of Φ25mm×240mm, evacuate to 10 -5Pa, sealed with a hydrogen-oxygen flame, placed in a muffle furnace, slowly heated to a temperature of 970 °C, held at a constant temperature for 64 h, then slowly cooled to 800 °C at a rate of 4 °C / h, and then cooled to room temperature at a rate of 16 °C / h. The muffle furnace was turned off. After the quartz tube cooled, it was cut open to obtain a Φ6×3 mm red mercury magnesium gallium selenide infrared nonlinear optical crystal.

[0108] Example 18

[0109] For the growth of the mercury magnesium gallium selenide infrared nonlinear optical crystal by the high-temperature melt method, the specific operation is carried out according to the following steps:

[0110] The pure sample of mercury magnesium gallium selenide powder obtained in Example 6 was loaded into a quartz tube with a diameter of Φ25 mm × 240 mm, evacuated to 10 -5 Pa, sealed with a hydrogen-oxygen flame, placed in a muffle furnace, slowly heated to a temperature of 980 °C, held at a constant temperature for 62 h, then slowly cooled to 800 °C at a rate of 4 °C / h, and then cooled to room temperature at a rate of 14 °C / h. The muffle furnace was turned off. After the quartz tube cooled, it was cut open to obtain a Φ6×4 mm red mercury magnesium gallium selenide infrared nonlinear optical crystal.

[0111] Example 19

[0112] For the growth of the mercury magnesium gallium selenide infrared nonlinear optical crystal by the high-temperature melt method, the specific operation is carried out according to the following steps:

[0113] The pure sample of mercury magnesium gallium selenide powder obtained in Example 7 was loaded into a quartz tube with a diameter of Φ25 mm × 240 mm, evacuated to 10 -5 Pa, sealed with a hydrogen-oxygen flame, placed in a muffle furnace, slowly heated to a temperature of 990 °C, held at a constant temperature for 60 h, then slowly cooled to 800 °C at a rate of 3 °C / h, and then cooled to room temperature at a rate of 14 °C / h. The muffle furnace was turned off. After the quartz tube cooled, it was cut open to obtain a Φ4×2 mm red mercury magnesium gallium selenide infrared nonlinear optical crystal.

[0114] Example 20

[0115] For the growth of the mercury magnesium gallium selenide infrared nonlinear optical crystal by the high-temperature melt method, the specific operation is carried out according to the following steps:

[0116] The pure sample of mercury magnesium gallium selenide powder obtained in Example 8 was loaded into a quartz tube with a diameter of Φ25 mm × 240 mm, evacuated to 10 -5 Pa, sealed with a hydrogen-oxygen flame, placed in a muffle furnace, slowly heated to a temperature of 990 °C, held at a constant temperature for 60 h, then slowly cooled to 800 °C at a rate of 3 °C / h, and then cooled to room temperature at a rate of 12 °C / h. The muffle furnace was turned off. After the quartz tube cooled, it was cut open to obtain a Φ4×3 mm red mercury magnesium gallium selenide infrared nonlinear optical crystal.

[0117] Example 21

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

[0119] Load the pure sample of mercury magnesium gallium selenide powder obtained in Example 9 into a quartz tube with a size of Φ25mm×240mm, evacuate to 10 -5 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, slowly heat up to a temperature of 1000 °C, keep it at a constant temperature for 58 h, then slowly cool it to 800 °C at a rate of 2 °C / h, and then cool it to room temperature at a rate of 10 °C / h. Turn off the muffle furnace. After the quartz tube cools down, cut it open to obtain a Φ5×3mm red mercury magnesium gallium selenide infrared nonlinear optical crystal.

[0120] Example 22

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

[0122] Load the pure sample of mercury magnesium gallium selenide powder obtained in Example 10 into a quartz tube with a size of Φ25mm×240mm, evacuate to 10 -5 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, slowly heat up to a temperature of 1000 °C, keep it at a constant temperature for 56 h, then slowly cool it to 800 °C at a rate of 1 °C / h, and then cool it to room temperature at a rate of 10 °C / h. Turn off the muffle furnace. After the quartz tube cools down, cut it open to obtain a Φ5×4mm red mercury magnesium gallium selenide infrared nonlinear optical crystal.

[0123] Example 23

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

[0125] Load the pure sample of mercury magnesium gallium selenide powder obtained in Example 11 into a quartz tube with a size of Φ25mm×240mm, evacuate to 10 -5 Pa, seal it with a hydrogen-oxygen flame, place it in a muffle furnace, slowly heat up to a temperature of 1000 °C, keep it at a constant temperature for 54 h, then slowly cool it to 800 °C at a rate of 1 °C / h, and then cool it to room temperature at a rate of 12 °C / h. Turn off the muffle furnace. After the quartz tube cools down, cut it open to obtain a Φ6×4mm red mercury magnesium gallium selenide infrared nonlinear optical crystal.

[0126] Example 24

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

[0128] Load the pure sample of mercury magnesium gallium selenide powder obtained in Example 12 into a quartz tube with a size of Φ25mm×240mm, evacuate to 10 -5Pa, encapsulated with oxyhydrogen flame, placed in a muffle furnace, slowly heated to 1000°C, kept constant for 50 hours, then slowly cooled to 800°C room temperature at a rate of 1°C / h, and then cooled to room temperature at a rate of 15°C / h, the muffle furnace was closed, and the quartz tube was cut open after cooling to obtain a Φ6×3mm red gallium mercury magnesium selenide infrared nonlinear optical crystal.

[0129] Embodiment 25

[0130] The chemical vapor transport method for growing the GaSe-MnHg-Si infrared nonlinear optical crystal is specifically performed in the following steps:

[0131] The pure powder sample of selenium, gallium, mercury and magnesium obtained in Example 1 was mixed with the I element and placed in a Φ25 mm×240 mm quartz tube and evacuated to 10 -5 Pa, encapsulated with hydrogen-oxygen flame, placed in a tubular growth furnace with chemical vapor transport at 950℃ in the high temperature zone and 800℃ in the low temperature zone, and MgHgGa 4 Se 8 The crystal was grown by simultaneously raising the temperature to 950℃ in the high temperature zone and 800℃ in the low temperature zone at a rate of 15℃ / h. The growth cycle was 15 days. After the growth was completed, the temperature was slowly lowered to room temperature at a rate of 2℃ / h. The tubular growth furnace was closed and the quartz tube was cut open after cooling. A Φ5.2×3.3mm red gallium mercury magnesium selenide infrared nonlinear optical crystal was obtained at the low temperature end.

[0132] Embodiment 26

[0133] The chemical vapor transport method for growing the GaSe-MnHg-Si infrared nonlinear optical crystal is specifically performed in the following steps:

[0134] The pure powder sample of selenium, gallium, mercury and magnesium obtained in Example 2 was mixed with the I element and placed in a Φ25 mm×240 mm quartz tube and evacuated to 10 -5 Pa was encapsulated with hydrogen-oxygen flame and placed in a tubular growth furnace for chemical vapor transport at 970°C in the high temperature zone and 820°C in the low temperature zone. MgHgGa 4 Se 8 The crystal was grown by simultaneously raising the temperature to 970℃ in the high temperature zone and 820℃ in the low temperature zone at a rate of 18℃ / h. The growth cycle was 18 days. After the growth was completed, the temperature was slowly lowered to room temperature at a rate of 3℃ / h. The tubular growth furnace was closed and the quartz tube was cut open after cooling. A Φ5×3mm red gallium mercury magnesium selenide infrared nonlinear optical crystal was obtained at the low temperature end.

[0135] Embodiment 27

[0136] The chemical vapor transport method for growing the GaSe-MnHg-Si infrared nonlinear optical crystal is specifically performed in the following steps:

[0137] The pure powder sample of selenium, gallium, mercury and magnesium obtained in Example 3 was mixed with the I element and placed in a Φ25 mm×240 mm quartz tube and evacuated to 10 -5 Pa was encapsulated with hydrogen-oxygen flame and placed in a tubular growth furnace for chemical vapor transport at 990°C in the high temperature zone and 840°C in the low temperature zone. MgHgGa 4 Se 8 The crystal was grown by simultaneously raising the temperature to 990℃ in the high temperature zone and 840℃ in the low temperature zone at a rate of 20℃ / h. The growth cycle was 20 days. After the growth was completed, the temperature was slowly lowered to room temperature at a rate of 4℃ / h. The tubular growth furnace was closed and the quartz tube was cut open after cooling. A Φ5.5×3mm red gallium mercury magnesium selenide infrared nonlinear optical crystal was obtained at the low temperature end.

[0138] Embodiment 28

[0139] The chemical vapor transport method for growing the GaSe-MnHg-Si infrared nonlinear optical crystal is specifically performed in the following steps:

[0140] The pure powder sample of selenium, gallium, mercury and magnesium obtained in Example 4 was mixed with the I element and placed in a Φ25 mm×240 mm quartz tube and evacuated to 10 -5 Pa was encapsulated with hydrogen-oxygen flame and placed in a tubular growth furnace for chemical vapor transport at a high temperature of 1010°C and a low temperature of 860°C. MgHgGa 4 Se 8 The crystal was grown by simultaneously raising the temperature to 1010℃ in the high temperature zone and 860℃ in the low temperature zone at a rate of 22℃ / h. The growth cycle was 23 days. After the growth was completed, the temperature was slowly lowered to room temperature at a rate of 5℃ / h. The tubular growth furnace was closed and the quartz tube was cut open after cooling. A Φ5.5×3.5mm red gallium mercury magnesium selenide infrared nonlinear optical crystal was obtained at the low temperature end.

[0141] Embodiment 29

[0142] The chemical vapor transport method for growing the GaSe-MnHg-Si infrared nonlinear optical crystal is specifically performed in the following steps:

[0143] The pure powder sample of selenium, gallium, mercury and magnesium obtained in Example 5 was mixed with the I element and placed in a Φ25 mm×240 mm quartz tube and evacuated to 10 -5 Pa was encapsulated with hydrogen-oxygen flame and placed in a tubular growth furnace for chemical vapor transport at a high temperature of 1030°C and a low temperature of 880°C. MgHgGa 4 Se 8The crystal was grown by simultaneously raising the temperature to 1030℃ in the high temperature zone and 880℃ in the low temperature zone at a rate of 25℃ / h. The growth cycle was 25 days. After the growth was completed, the temperature was slowly lowered to room temperature at a rate of 6℃ / h. The tubular growth furnace was closed and the quartz tube was cut open after cooling. A Φ5×4mm red gallium mercury magnesium selenide infrared nonlinear optical crystal was obtained at the low temperature end.

[0144] Embodiment 30

[0145] The chemical vapor transport method for growing the GaSe-MnHg-Si infrared nonlinear optical crystal is specifically performed in the following steps:

[0146] The pure powder sample of selenium, gallium, mercury and magnesium obtained in Example 6 was mixed with the I element and placed in a Φ25 mm×240 mm quartz tube and evacuated to 10 -5 Pa was encapsulated with hydrogen-oxygen flame and placed in a tubular growth furnace for chemical vapor transport at 1030°C in the high temperature zone and 880°C in the low temperature zone. MgHgGa 4 Se 8 The crystal was grown by simultaneously raising the temperature to 1030℃ in the high temperature zone and 880℃ in the low temperature zone at a rate of 25℃ / h. The growth cycle was 25 days. After the growth was completed, the temperature was slowly lowered to room temperature at a rate of 6℃ / h. The tubular growth furnace was closed and the quartz tube was cut open after cooling. A Φ5.5×4mm red gallium mercury magnesium selenide infrared nonlinear optical crystal was obtained at the low temperature end.

[0147] Embodiment 31

[0148] The chemical vapor transport method for growing the GaSe-MnHg-Si infrared nonlinear optical crystal is specifically performed in the following steps:

[0149] The pure powder sample of selenium, gallium, mercury and magnesium obtained in Example 7 was mixed with the I element and placed in a Φ25 mm×240 mm quartz tube and evacuated to 10 -5 Pa, encapsulated with hydrogen-oxygen flame, placed in a tubular growth furnace with a high temperature zone of 1050 ° C and a low temperature zone of 900 ° C for chemical vapor transport, and MgHgGa 4 Se 8 The crystal was grown by simultaneously raising the temperature to 1050℃ in the high temperature zone and 900℃ in the low temperature zone at a rate of 25℃ / h. The growth cycle was 28 days. After the growth was completed, the temperature was slowly lowered to room temperature at a rate of 7℃ / h. The tubular growth furnace was closed and the quartz tube was cut open after cooling. A Φ6×4mm red gallium mercury magnesium selenide infrared nonlinear optical crystal was obtained at the low temperature end.

[0150] Embodiment 32

[0151] The chemical vapor transport method for growing the GaSe-MnHg-Si infrared nonlinear optical crystal is specifically performed in the following steps:

[0152] Mix the pure sample of magnesium mercury gallium selenide powder obtained in Example 8 with I element and load it into a quartz tube with a size of Φ25mm×240mm. Evacuate it to 10 -5 Pa, seal it with a hydrogen-oxygen flame, place it in a tube furnace, and perform chemical vapor transport at a high-temperature zone of 1070°C and a low-temperature zone of 900°C. Conduct crystal growth of MgHgGa 4 Se 8 by means of a horizontal gradient temperature field. Heat it up to 1050°C in the high-temperature zone and 900°C in the low-temperature zone at a rate of 25°C / h simultaneously. The growth period is 30 days. After the growth is completed, slowly cool it down to room temperature at a rate of 8°C / h. Turn off the tube furnace. After the quartz tube cools down, cut it open to obtain a Φ6×4mm red magnesium mercury gallium selenide infrared nonlinear optical crystal at the low-temperature end.

[0153] Example 33

[0154] For growing the magnesium mercury gallium selenide infrared nonlinear optical crystal by the chemical vapor transport method, the specific operation is carried out according to the following steps:

[0155] Mix the pure sample of magnesium mercury gallium selenide powder obtained in Example 9 with I element and load it into a quartz tube with a size of Φ25mm×240mm. Evacuate it to 10 -5 Pa, seal it with a hydrogen-oxygen flame, place it in a tube furnace, and perform chemical vapor transport at a high-temperature zone of 1090°C and a low-temperature zone of 900°C. Conduct crystal growth of MgHgGa 4 Se 8 by means of a horizontal gradient temperature field. Heat it up to 1090°C in the high-temperature zone and 900°C in the low-temperature zone at a rate of 25°C / h simultaneously. The growth period is 32 days. After the growth is completed, slowly cool it down to room temperature at a rate of 9°C / h. Turn off the tube furnace. After the quartz tube cools down, cut it open to obtain a Φ7×4mm red magnesium mercury gallium selenide infrared nonlinear optical crystal at the low-temperature end.

[0156] Example 34

[0157] For growing the magnesium mercury gallium selenide infrared nonlinear optical crystal by the chemical vapor transport method, the specific operation is carried out according to the following steps:

[0158] Mix the pure sample of magnesium mercury gallium selenide powder obtained in Example 10 with I element and load it into a quartz tube with a size of Φ25mm×240mm. Evacuate it to 10 -5 Pa, seal it with a hydrogen-oxygen flame, place it in a tube furnace, and perform chemical vapor transport at a high-temperature zone of 1100°C and a low-temperature zone of 900°C. Conduct crystal growth of MgHgGa 4 Se 8The crystal was grown by simultaneously raising the temperature to 1100℃ in the high temperature zone and 900℃ in the low temperature zone at a rate of 25℃ / h. The growth cycle was 35 days. After the growth was completed, the temperature was slowly lowered to room temperature at a rate of 9℃ / h. The tubular growth furnace was closed and the quartz tube was cut open after cooling. A Φ7×5mm red gallium mercury magnesium selenide infrared nonlinear optical crystal was obtained at the low temperature end.

[0159] Embodiment 35

[0160] The chemical vapor transport method for growing the GaSe-MnHg-Si infrared nonlinear optical crystal is specifically performed in the following steps:

[0161] The pure powder sample of selenium, gallium, mercury and magnesium obtained in Example 11 was mixed with the I element and placed in a Φ25 mm×240 mm quartz tube and evacuated to 10 -5 Pa, encapsulated with hydrogen-oxygen flame, placed in a tubular growth furnace with a high temperature zone of 1050 ° C and a low temperature zone of 900 ° C for chemical vapor transport, and MgHgGa 4 Se 8 The crystal was grown by simultaneously raising the temperature to 1050℃ in the high temperature zone and 900℃ in the low temperature zone at a rate of 20℃ / h. The growth cycle was 35 days. After the growth was completed, the temperature was slowly lowered to room temperature at a rate of 6℃ / h. The tubular growth furnace was closed and the quartz tube was cut open after cooling. A Φ7.5×5mm red gallium mercury magnesium selenide infrared nonlinear optical crystal was obtained at the low temperature end.

[0162] Embodiment 36

[0163] The chemical vapor transport method for growing the GaSe-MnHg-Si infrared nonlinear optical crystal is specifically performed in the following steps:

[0164] The pure powder sample of selenium, gallium, mercury and magnesium obtained in Example 12 was mixed with the I element and placed in a Φ25 mm×240 mm quartz tube and evacuated to 10 -5 Pa, encapsulated with hydrogen-oxygen flame, placed in a tubular growth furnace with a high temperature zone of 1000 ° C and a low temperature zone of 850 ° C for chemical vapor transport, and MgHgGa 4 Se 8 The crystal was grown by simultaneously raising the temperature 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 lowered to room temperature at a rate of 6℃ / h. The tubular growth furnace was closed and the quartz tube was cut open after cooling. A Φ7×5mm red gallium mercury magnesium selenide infrared nonlinear optical crystal was obtained at the low temperature end.

[0165] Embodiment 37

[0166] The crucible descent method for growing the GaMgSe infrared nonlinear optical crystal is specifically performed in the following steps:

[0167] The pure sample of mercury magnesium gallium selenide powder obtained in Example 1 was loaded into a quartz tube with a size of Φ25mm×240mm, evacuated to 10 -5 Pa, then sealed with a hydrogen-oxygen flame, placed in a crucible descending furnace, heated to 950°C at a rate of 5°C / h, held at a constant temperature for 90h until the raw materials were completely melted, and then the crucible descending furnace was vertically lowered at a speed of 1mm / h. During the descent, crystal growth of MgHgGa 4 Se 8 was carried out. The growth period was 15 days. After the crystal growth was completed, the crystal was left in the crucible descending furnace for annealing, cooled to room temperature at a rate of 40°C / h, and a red mercury magnesium gallium selenide infrared nonlinear optical crystal with a size of Φ6×3mm was obtained.

[0168] Example 38

[0169] For the growth of mercury magnesium gallium selenide infrared nonlinear optical crystal by the crucible descending method, the specific operation is carried out according to the following steps:

[0170] The pure sample of mercury magnesium gallium selenide powder obtained in Example 2 was loaded into a quartz tube with a size of Φ25mm×240mm, evacuated to 10 -5 Pa, then sealed with a hydrogen-oxygen flame, placed in a crucible descending furnace, heated to 960°C at a rate of 8°C / h, held at a constant temperature for 85h until the raw materials were completely melted, and then the crucible descending furnace was vertically lowered at a speed of 1.2mm / h. During the descent, crystal growth of MgHgGa 4 Se 8 was carried out. The growth period was 18 days. After the crystal growth was completed, the crystal was left in the crucible descending furnace for annealing, cooled to room temperature at a rate of 36°C / h, and a red mercury magnesium gallium selenide infrared nonlinear optical crystal with a size of Φ6.5×2.5mm was obtained.

[0171] Example 39

[0172] For the growth of mercury magnesium gallium selenide infrared nonlinear optical crystal by the crucible descending method, the specific operation is carried out according to the following steps:

[0173] The pure sample of mercury magnesium gallium selenide powder obtained in Example 3 was loaded into a quartz tube with a size of Φ25mm×240mm, evacuated to 10 -5 Pa, then sealed with a hydrogen-oxygen flame, placed in a crucible descending furnace, heated to 960°C at a rate of 10°C / h, held at a constant temperature for 80h until the raw materials were completely melted, and then the crucible descending furnace was vertically lowered at a speed of 1.5mm / h. During the descent, crystal growth of MgHgGa 4 Se 8 was carried out. The growth period was 20 days. After the crystal growth was completed, the crystal was left in the crucible descending furnace for annealing, cooled to room temperature at a rate of 34°C / h, and a red mercury magnesium gallium selenide infrared nonlinear optical crystal with a size of Φ5×2.5mm could be obtained.

[0174] Example 40

[0175] For the growth of HgMgGaSe infrared nonlinear optical crystal by the Bridgman method, the specific operation is carried out according to the following steps:

[0176] Load the pure HgMgGaSe powder sample obtained in Example 4 into a quartz tube with a diameter of Φ25mm×240mm, evacuate to 10 -5 Pa, then seal it with a hydrogen-oxygen flame, place it in a Bridgman furnace, heat it to 970℃ at a rate of 12℃ / h, keep it at a constant temperature for 75h until the raw materials are completely melted, and then lower the Bridgman furnace vertically at a speed of 1.8mm / h. During the lowering process, crystal growth of MgHgGa 4 Se 8 is carried out. The growth period is 20 days. After the crystal growth is completed, the crystal is left in the Bridgman furnace for annealing and cooled to room temperature at a rate of 32℃ / h to obtain a Φ5×3mm red HgMgGaSe infrared nonlinear optical crystal.

[0177] Example 41

[0178] For the growth of HgMgGaSe infrared nonlinear optical crystal by the Bridgman method, the specific operation is carried out according to the following steps:

[0179] Load the pure HgMgGaSe powder sample obtained in Example 5 into a quartz tube with a diameter of Φ25mm×240mm, evacuate to 10 -5 Pa, then seal it with a hydrogen-oxygen flame, place it in a Bridgman furnace, heat it to 980℃ at a rate of 15℃ / h, keep it at a constant temperature for 75h until the raw materials are completely melted, and then lower the Bridgman furnace vertically at a speed of 2mm / h. During the lowering process, crystal growth of MgHgGa 4 Se 8 is carried out. The growth period is 25 days. After the crystal growth is completed, the crystal is left in the Bridgman furnace for annealing and cooled to room temperature at a rate of 30℃ / h to obtain a Φ5.5×3mm red HgMgGaSe infrared nonlinear optical crystal.

[0180] Example 42

[0181] For the growth of HgMgGaSe infrared nonlinear optical crystal by the Bridgman method, the specific operation is carried out according to the following steps:

[0182] Load the pure HgMgGaSe powder sample obtained in Example 6 into a quartz tube with a diameter of Φ25mm×240mm, evacuate to 10 -5 Pa, then seal it with a hydrogen-oxygen flame, place it in a Bridgman furnace, heat it to 980℃ at a rate of 17℃ / h, keep it at a constant temperature for 70h until the raw materials are completely melted, and then lower the Bridgman furnace vertically at a speed of 2.2mm / h. During the lowering process, crystal growth of MgHgGa 4 Se 8The crystal growth takes 25 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 28 °C / h to obtain a Φ5×2.5 mm red HgMgGaSe infrared nonlinear optical crystal.

[0183] Example 43

[0184] For the growth of HgMgGaSe infrared nonlinear optical crystal by the crucible drop method, the specific operation is carried out according to the following steps:

[0185] The pure sample of HgMgGaSe powder obtained in Example 7 is loaded into a quartz tube with a size of Φ25 mm×240 mm, evacuated to 10 -5 Pa and then sealed with a hydrogen-oxygen flame. It is placed in a crucible drop furnace and heated to 990 °C at a rate of 20 °C / h, held at a constant temperature for 68 h until the raw materials are completely melted. Then the crucible drop furnace is vertically lowered at a speed of 2.5 mm / h. During the lowering process, the crystal growth of MgHgGa 4 Se 8 takes place. The growth period is 25 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 25 °C / h to obtain a Φ4×2.5 mm red HgMgGaSe infrared nonlinear optical crystal.

[0186] Example 44

[0187] For the growth of HgMgGaSe infrared nonlinear optical crystal by the crucible drop method, the specific operation is carried out according to the following steps:

[0188] The pure sample of HgMgGaSe powder obtained in Example 8 is loaded into a quartz tube with a size of Φ25 mm×240 mm, evacuated to 10 -5 Pa and then sealed with a hydrogen-oxygen flame. It is placed in a crucible drop furnace and heated to 1000 °C at a rate of 20 °C / h, held at a constant temperature for 60 h until the raw materials are completely melted. Then the crucible drop furnace is vertically lowered at a speed of 2.8 mm / h. During the lowering process, the crystal growth of MgHgGa 4 Se 8 takes place. The growth period is 20 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 25 °C / h to obtain a Φ3×2.5 mm red HgMgGaSe infrared nonlinear optical crystal.

[0189] Example 45

[0190] For the growth of HgMgGaSe infrared nonlinear optical crystal by the crucible drop method, the specific operation is carried out according to the following steps:

[0191] The pure sample of HgMgGaSe powder obtained in Example 9 is loaded into a quartz tube with a size of Φ25 mm×240 mm, evacuated to 10 -5After reaching 10 Pa, it is sealed with a hydrogen-oxygen flame and placed in a descending crucible furnace. It is heated to 980 °C at a rate of 20 °C / h, held at a constant temperature of 65 h until the raw materials are completely melted. Then, the descending crucible furnace is vertically lowered at a speed of 3 mm / h. During the descent, the crystal growth of MgHgGa 4 Se 8 is carried out. The growth period is 15 days. After the crystal growth is completed, the crystal is left in the descending crucible furnace for annealing and cooled to room temperature at a rate of 20 °C / h to obtain a Φ3×2 mm red mercury magnesium gallium selenide infrared nonlinear optical crystal.

[0192] Example 46

[0193] For the growth of mercury magnesium gallium selenide infrared nonlinear optical crystal by the descending crucible method, the specific operation is carried out according to the following steps:

[0194] The pure sample of mercury magnesium gallium selenide powder obtained in Example 10 is loaded into a quartz tube with a size of Φ25 mm×240 mm, evacuated to 10 -5 Pa, then sealed with a hydrogen-oxygen flame, placed in a descending crucible furnace, heated to 980 °C at a rate of 20 °C / h, held at a constant temperature of 80 h until the raw materials are completely melted. Then, the descending crucible furnace is vertically lowered at a speed of 3 mm / h. During the descent, the crystal growth of MgHgGa 4 Se 8 is carried out. The growth period is 18 days. After the crystal growth is completed, the crystal is left in the descending crucible furnace for annealing and cooled to room temperature at a rate of 30 °C / h to obtain a Φ4×2.5 mm red mercury magnesium gallium selenide infrared nonlinear optical crystal.

[0195] Example 47

[0196] For the growth of mercury magnesium gallium selenide infrared nonlinear optical crystal by the descending crucible method, the specific operation is carried out according to the following steps:

[0197] The pure sample of mercury magnesium gallium selenide powder obtained in Example 11 is loaded into a quartz tube with a size of Φ25 mm×240 mm, evacuated to 10 -5 Pa, then sealed with a hydrogen-oxygen flame, placed in a descending crucible furnace, heated to 980 °C at a rate of 15 °C / h, held at a constant temperature of 70 h until the raw materials are completely melted. Then, the descending crucible furnace is vertically lowered at a speed of 2 mm / h. During the descent, the crystal growth of MgHgGa 4 Se 8 is carried out. The growth period is 20 days. After the crystal growth is completed, the crystal is left in the descending crucible furnace for annealing and cooled to room temperature at a rate of 30 °C / h to obtain a Φ5×3 mm red mercury magnesium gallium selenide infrared nonlinear optical crystal.

[0198] Example 48

[0199] The growth of HgMgGaSe infrared nonlinear optical crystal by the Bridgman method is carried out according to the following steps:

[0200] The pure HgMgGaSe powder obtained in Example 12 is loaded into a quartz tube with a diameter of 25 mm and a length of 240 mm. After evacuating to 10 -5 Pa, it is sealed with a hydrogen-oxygen flame and placed in a Bridgman furnace. It is heated to 980 °C at a rate of 15 °C / h and kept at a constant temperature for 60 h until the raw materials are completely melted. Then the Bridgman furnace is vertically lowered at a speed of 1.5 mm / h. During the lowering process, the crystal growth of MgHgGa 4 Se 8 is carried out. The growth period is 20 days. After the crystal growth is completed, the crystal is left in the Bridgman furnace for annealing and cooled to room temperature at a rate of 40 °C / h to obtain a HgMgGaSe infrared nonlinear optical crystal with a diameter of Φ6×2.5 mm and a red color.

[0201] Example 49

[0202] Any one of the HgMgGa 4 Se 8 infrared nonlinear optical crystals obtained in Examples 13-48 is placed at the position labeled 3 in the Figure 4 shown device. At room temperature, a Q-switched Ho:Tm:Cr:YAG laser is used as the light source, and infrared light with an incident wavelength of 2090 nm is used to generate second-harmonic light with an output wavelength of 1045 nm. The laser intensity output by the HgMgGa 4 Se 8 crystal is 1.8 times the output intensity of AgGaS 2 under the same conditions.

[0203] Example 50

[0204] Any one of the HgMgGa 4 Se 8 infrared nonlinear optical crystals obtained in Examples 13-48 is placed at the position of 3 as shown in Figure 4 . Among them, 1 is a laser, 2 is a convex lens, 3 is a HgMgGa 4 Se 8 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 HgMgGa 4 Se 8 crystal 3. The generated output laser beam passes through the prism 4 and the filter 5 to obtain the required laser beam.

[0205] Using the HgMgGa 4 Se 8Devices made of infrared nonlinear optical crystals can be frequency doubling generators, up and 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 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, gallium, mercury and magnesium, characterized in that The molecular formula of the compound is MgHgGa4Se8, the molecular weight is 1135.46 g / mol, it belongs to the tetragonal system, and crystallizes in the non-central space group of Made by high temperature solid phase method.

2. The method for preparing the compound of selenium gallium mercury magnesium according to claim 1, characterized in that The molecular formula of the compound is MgHgGa4Se8, and it is prepared by a high-temperature solid phase method. The specific operation is carried out in the following steps: a. The molar ratio of Mg:Hg:Ga:Se=1:1:4:8 is as follows: Mg source material is Mg or MgSe; Hg source material is Hg or HgSe; Ga source material is Ga, GaSe or Ga2Se3 and elemental Se are mixed evenly, ground, put into a Φ25mm×240mm quartz container, and evacuated to 10 -3 -10 -5 Pa and perform fusion sealing; b. Place the sealed sample in step a in a muffle furnace, heat it to 800-920°C at a rate of 10-40°C / h, keep it at a constant temperature for 60-80 hours, then reduce it to 400°C at a rate of 10-20°C / h, and then cool it naturally to room temperature. After cooling, take out the sample, crush it and grind it to obtain a powdered MgHgGa4Se8 compound.

3. A gallium-mercury-magnesium-selenide infrared nonlinear optical crystal, characterized in that: The crystal has a molecular formula of MgHgGa4Se8, a molecular weight of 1135.46 g / mol, has no symmetry center, belongs to the tetragonal system, and has a space group of The unit cell parameters are α=β=γ=90°, Z=1.

4. The method for preparing the gallium-mercury-magnesium-selenide infrared nonlinear optical crystal according to claim 3, characterized in that Crystal growth using high temperature melt method, chemical vapor transport method or crucible descent method: The high temperature melt method for growing the infrared nonlinear optical crystal of gallium, mercury and magnesium selenium is specifically carried out in the following steps: a. The molar ratio of Mg:Hg:Ga:Se=1:1:4:8 is as follows: Mg source material is Mg or MgSe; Hg source material is Hg or HgSe; Ga source material is Ga, GaSe or Ga2Se3 and single substance Se are mixed evenly, loaded into a Φ25mm×240mm quartz tube, and evacuated to 10 -3 -10 -5 Pa and sealed, put into a muffle furnace, heat to 800-920℃ at a rate of 10-40℃ / h, keep constant temperature for 60-80h, then reduce to 400℃ at 10-20℃ / h, then naturally cool to room temperature, take out the sample, crush and grind to obtain a pure sample of powdered MgHgGa4Se8; b. Put the obtained pure sample powder into a quartz tube and evacuate to 10 -3 -10 -5 Pa, encapsulated with hydrogen-oxygen flame, placed in a muffle furnace, slowly raised to 930-1000°C, kept constant for 48-72h, then slowly dropped to 800°C at a rate of 1-5°C / h, and then dropped to room temperature at a rate of 10-20°C / h, the muffle furnace was closed, 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 infrared nonlinear optical crystal of gallium, mercury and magnesium selenium is specifically performed in the following steps: a. The molar ratio of Mg:Hg:Ga:Se=1:1:4:8 is as follows: Mg source material is Mg or MgSe; Hg source material is Hg or HgSe; Ga source material is Ga, GaSe or Ga2Se3 and single substance Se are mixed evenly, loaded into a Φ25mm×240mm quartz tube, and evacuated to 10 -3 -10 -5 Pa, encapsulated with hydrogen-oxygen flame, placed in a muffle furnace, heated to 800-920°C at a rate of 10-40°C / h, kept at a constant temperature for 60-80h, then cooled to 400°C at a rate of 10-20°C / h, then naturally cooled to room temperature, took out the sample, crushed and ground to obtain a pure sample of powdered MgHgGa4Se8; b. Mix the obtained pure sample powder with I single substance in a tubular growth furnace for chemical vapor transmission, wherein the high temperature zone is 950-1100°C and the low temperature zone is 800-900°C, and grow the crystal of MgHgGa4Se8 through a horizontal or vertical gradient temperature field, and heat it to 950-1100°C in the high temperature zone and 800-900°C in the low temperature zone at a rate of 15-25°C / h at the same time, and the growth cycle is 15-35 days. After the growth is completed, slowly cool it to room temperature at a rate of 2-9°C / h, close the tubular growth furnace, wait for the quartz tube to cool down and then cut it, and obtain a red MgHgGa4Se8 infrared nonlinear optical crystal at the low temperature end; The crucible descent method for growing the GaMgSe infrared nonlinear optical crystal is specifically performed in the following steps: a. The molar ratio of Mg:Hg:Ga:Se=1:1:4:8 is as follows: Mg source material is Mg or MgSe; Hg source material is Hg or HgSe; Ga source material is Ga, GaSe or Ga2Se3 and single substance Se are mixed evenly, loaded into a Φ25mm×240mm quartz tube, and evacuated to 10 -3 -10 -5 Pa, encapsulated with hydrogen-oxygen flame, placed in a muffle furnace, heated to 800-920°C at a rate of 10-40°C / h, kept at a constant temperature for 60-80h, then cooled to 400°C at a rate of 10-20°C / h, then naturally cooled to room temperature, took out the sample, crushed and ground to obtain a pure sample of powdered MgHgGa4Se8; b. Put the obtained pure sample powder into a quartz tube and evacuate to 10 -3 -10 -5 Pa, encapsulated with oxyhydrogen flame, placed in a crucible descending furnace, heated to 940-1000°C at 5-20°C / h, kept at a constant temperature for 60-100h until the raw materials are completely melted, and then the crucible descending furnace is vertically lowered at a speed of 1-3mm / h. Crystal growth is carried out during the descending process, and the growth cycle is 15-25 days. After the crystal growth is completed, the crystal is left in the crucible descending furnace for annealing, and cooled to room temperature at a rate of 20-40°C / h to obtain a red MgHgGa4Se8 infrared nonlinear optical crystal.

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

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