Compound zinc mercury gallium selenium and zinc mercury gallium selenium far-infrared nonlinear optical crystal, preparation method and application thereof

Abstract

The application provides a compound zinc mercury gallium selenium and a far-infrared nonlinear optical crystal of zinc mercury gallium selenium, a preparation method and an application, the compound has a chemical formula of Zn 0.8 Hg 0.2 Ga2Se4, a molecular weight of 547.71, the crystal has a chemical formula of Zn 0.8 Hg 0.2 Ga2Se4, a molecular weight of 547.71, is a tetragonal crystal, and a space group is a non-central symmetry space group I -4, cell parameters are a=5.5627(6)Å, b=5.5627(6)Å, c=10.881(2)Å, alpha=beta=gamma=90°, Z=2, and a unit cell volume V=336.69(8)Å 3 ; a powder pure sample and a single crystal are prepared by a solid phase reaction under vacuum conditions; the pure sample XRD graph of the zinc mercury gallium selenium infrared nonlinear optical crystal in the application is consistent with a theoretical value; the crystal band gap is 2.3 eV, and the ultraviolet cutoff edge is 489 nm, which are measured by using ultraviolet-visible diffuse reflection spectroscopy; under laser irradiation at 2090 nm, the Zn 0.8 Hg 0.2 Ga2Se4 with a particle size of 0.105-0.15 microns has a frequency doubling effect which is 4 times that of commercialized silver gallium sulfide (AgGaS2).

Description

Technical Field

[0001] This invention belongs to the field of infrared nonlinear optical crystal materials, specifically relating to a zinc mercury gallium selenide (ZMS) and ZMS mid-far-infrared nonlinear optical crystals, their preparation methods, and applications. Background Technology

[0002] Nonlinear optical crystal materials can be classified into three main categories based on their transmission wavelength range: 1. Nonlinear optical materials in the ultraviolet and deep ultraviolet bands; 2. Nonlinear optical materials in the visible and near-infrared bands; and 3. Nonlinear optical materials in the infrared and mid-to-far-infrared bands. This invention pertains to nonlinear optical materials in the visible and mid-to-far-infrared bands. Nonlinear optical crystal materials in this band have wide applications, such as in laser frequency converters, infrared lidar, laser communication, infrared filtering devices, and optoelectronic countermeasures.

[0003] To date, the generation of 3-20μm solid-state mid-to-far infrared lasers is mainly based on nonlinear optics principles and infrared nonlinear optical crystal frequency conversion technology. Common infrared nonlinear optical crystals on the market include AgGaS2, AgGaSe2, and ZnGeP2. Although these crystals have been used in civilian production, high-tech fields, and military equipment, these crystal materials also have their own shortcomings, and their overall performance still cannot meet ideal requirements. With technological advancements and increasing demands, the need for higher-performance infrared nonlinear crystals is becoming more urgent. Therefore, the exploration of new mid-to-far infrared nonlinear crystals has significant strategic importance for both civilian high-tech industries and the improvement of military equipment. Furthermore, the synthesis and growth of crystal materials represent a significant challenge in this direction. Summary of the Invention

[0004] The purpose of this invention is to provide a compound zinc mercury gallium selenide (ZMGS) and a far-infrared nonlinear optical crystal, as well as their preparation methods and applications. The chemical formula of the compound is Zn. 0.8 Hg 0.2 Ga2Se4, with a molecular weight of 547.71, has the chemical formula Zn. 0.8 Hg 0.2 Ga2Se4, with a molecular weight of 547.71, belongs to the tetragonal crystal system and has a non-centrosymmetric space group I-4. Its unit cell parameters are... α=β=γ=90°, Z=2, unit cell volume The preparation method includes the solid-state reaction of zinc selenide, mercuric selenide, and gallium selenide under vacuum conditions; the powder XRD patterns of the zinc-mercury-gallium-selenide and the far-infrared nonlinear optical crystals of the present invention are in good agreement with the theoretical values; under 2090 nm laser irradiation, Zn with a particle size of 0.105-0.15 μm... 0.8 Hg0.2 The frequency multiplication effect of Ga2Se4 is 4 times that of commercially available AgGaS2.

[0005] The present invention discloses a compound, zinc mercury gallium selenide, with the chemical formula Zn. 0.8 Hg 0.2 Ga₂Se₄, with a molecular weight of 547.71, is a non-centrosymmetric single crystal with a tetragonal crystal system, space group I-4, and cell parameters [not specified]. α=β=γ=90°, Z=2, unit cell volume

[0006] A zinc-mercury-gallium-selenium mid-far-infrared nonlinear optical crystal, the chemical formula of which is Zn 0.8 Hg 0.2 Ga2Se4, with a molecular weight of 547.71, is a non-centrosymmetric single crystal with a tetragonal crystal system, space group I-4, and cell parameters [not specified]. α=β=γ=90°, Z=2, unit cell volume

[0007] The zinc-mercury-gallium-selenium far-infrared nonlinear optical crystal is prepared using a vacuum tube sealing method, and the specific operation is carried out according to the following steps:

[0008] a. In a sealed glove box filled with inert gas and containing 0.01-0.1 ppm of both water and oxygen, ZnSe, HgSe, and Ga2Se3 are weighed and mixed thoroughly in a mass ratio of 4:5:5. The mixture is then placed into a quartz glass tube, and the tube is placed under a vacuum of 10... -5 -10 -3 After vacuuming, Pa is sealed, and the inert gas is argon.

[0009] b. Place the sealed quartz tube from step a into a high-temperature furnace and raise the temperature to 1000-1150℃ at a rate of 30-40℃ / h, and keep it at that temperature for 100h.

[0010] c. Then cool to room temperature at a rate of 3-5℃ / h to obtain zinc mercury gallium selenide (Zn). 0.8 Hg 0.2 Ga2Se4 mid-to-far infrared nonlinear optical crystal.

[0011] In the preparation method of the zinc-mercury-gallium-selenium far-infrared nonlinear optical crystal, the cooling rate of the compound in step c is 4℃ / h.

[0012] Applications of the zinc-mercury-gallium-selenium mid-infrared nonlinear optical crystal in the preparation of infrared band laser frequency conversion crystals, infrared electro-optic devices, infrared communication devices, or infrared laser guidance devices.

[0013] The zinc-mercury-gallium-selenide (ZMGS) far-infrared nonlinear optical crystal of this invention has the following crystal structure: Zn, Hg, Ga, and Se atoms have oxidation states of +2, +2, +3, and -2, respectively. Both Zn / Hg and Ga atoms form tetrahedral structures with four neighboring Se atoms. These two tetrahedra are stacked together through a shared selenium atom to form a diamond-like structure. The ZMGS compound is a single-crystal ZMGS particle. Attached Figure Description

[0014] Figure 1 This is a comparison diagram of the X-ray powder diffraction pattern of the polycrystalline powder of the present invention and the theoretical value, where A is the experimental value and B is the theoretical value;

[0015] Figure 2 For the present invention Zn 0.8 Hg 0.2 UV-Vis diffuse reflectance of Ga2Se4;

[0016] Figure 3 The compound Zn of this invention 0.8 Hg 0.2 Structural diagram of Ga2Se4 single crystal;

[0017] Figure 4 The compound Zn of this invention 0.8 Hg 0.2 Photograph of Ga2Se4 crystal;

[0018] Figure 5 For the present invention Zn 0.8 Hg 0.2 A schematic diagram illustrating the working principle of a nonlinear optical device fabricated from Ga2Se4 crystal, where 1 represents the laser, 2 represents the emitted beam, and 3 represents Zn. 0.8 Hg 0.2 Ga2Se4 crystal, 4 is the emitted beam, 5 is the filter. Detailed Implementation

[0019] This invention relates to the compounds zinc mercury gallium selenide (ZMS) and ZMS far-infrared nonlinear optical crystals, their preparation methods, and applications. Both the polycrystalline ZMS powder and single crystal are prepared using a closed-system high-temperature solid-state reaction method, but their process parameters differ significantly. In the polycrystalline powder synthesis process, the isothermal sintering temperature is set at 950℃, with a heating rate of 92℃ / h and a cooling rate of 38℃ / h. Single crystal growth, however, requires a temperature range of 1000-1100℃, with a controlled heating rate of 30-40℃ / h and a precise cooling rate of 4-5℃ / h. This invention is described in detail through examples, but is not limited to the given examples.

[0020] Example 1

[0021] Preparation of zinc-mercury-gallium-selenium polycrystalline powder:

[0022] a. In a glove box filled with inert gas and containing 0.1 ppm of both water and oxygen, weigh out Zn, HgSe, Ga2Se3 and Se according to the molar ratio of Zn:HgSe:Ga2Se3:Se 4:1:5:4, mix them evenly, and then put them into a quartz glass tube. After evacuating the quartz tube, seal it.

[0023] b. Place the sealed quartz tube from step a into a high-temperature furnace, raise the temperature to 950℃ over 10 hours, hold it at that temperature for 24 hours, and then rapidly cool it to room temperature over 24 hours to obtain orange polycrystalline powder. Perform X-ray powder diffraction on the prepared polycrystalline phase; the results are shown in [reference needed]. Figure 1 As can be seen from the figure, the experimental value is close to the theoretical value, indicating that the obtained powder sample is a pure phase.

[0024] Example 2

[0025] The preparation method of the zinc-mercury-gallium-selenium far-infrared nonlinear optical crystal is carried out according to the following steps:

[0026] a. In a glove box filled with inert gas and sealed container containing 0.01 ppm of both water and oxygen, ZnSe, HgSe, and Ga2Se3 are weighed and mixed thoroughly in a mass ratio of 4:5:5. The mixture is then placed into a quartz glass tube, and the tube is placed under a vacuum of 10... -5 -10 -3 After vacuuming, Pa is sealed, and the inert gas is argon.

[0027] b. Place the sealed quartz tube from step a into a high-temperature furnace and raise the temperature to 1000℃ at a rate of 30℃ / h, and hold for 100h.

[0028] c. Then cool to room temperature at a rate of 3℃ / h to obtain zinc mercury gallium selenide (Zn) with dimensions of 0.2mm × 0.5mm × 0.5mm. 0.8 Hg 0.2 Ga2Se4 mid-to-far infrared nonlinear optical crystal.

[0029] Example 3

[0030] The preparation method of the zinc-mercury-gallium-selenium far-infrared nonlinear optical crystal is carried out according to the following steps:

[0031] a. In a glove box filled with inert gas and sealed container containing 0.03 ppm of both water and oxygen, ZnSe, HgSe, and Ga2Se3 are weighed and mixed thoroughly in a mass ratio of 4:5:5. The mixture is then placed into a quartz glass tube, and the tube is placed under a vacuum of 10... -5 -10 -3 After vacuuming, Pa is sealed, and the inert gas is argon.

[0032] b. Place the sealed quartz tube from step a into a high-temperature furnace and raise the temperature to 1050℃ at a rate of 32℃ / h, and hold for 100h.

[0033] c. Then cool to room temperature at a rate of 4℃ / h to obtain zinc mercury gallium selenide (Zn) with dimensions of 0.3mm × 0.5mm × 0.6mm. 0.8 Hg 0.2 Ga2Se4 mid-to-far infrared nonlinear optical crystal.

[0034] Example 4

[0035] The preparation method of the zinc-mercury-gallium-selenium far-infrared nonlinear optical crystal is carried out according to the following steps:

[0036] a. In a glove box filled with inert gas and sealed container containing 0.05 ppm of both water and oxygen, ZnSe, HgSe, and Ga2Se3 are weighed and mixed thoroughly in a mass ratio of 4:5:5. The mixture is then placed into a quartz glass tube, and the tube is placed under a vacuum of 10... -5 -10 -3 After vacuuming, Pa is sealed, and the inert gas is argon.

[0037] b. Place the sealed quartz tube from step a into a high-temperature furnace and raise the temperature to 1080℃ at a rate of 35℃ / h, and hold for 100h.

[0038] c. Then cool to room temperature at a rate of 5℃ / h to obtain zinc mercury gallium selenide (Zn) with dimensions of 0.4mm × 0.3mm × 0.5mm. 0.8 Hg 0.2 Ga2Se4 mid-to-far infrared nonlinear optical crystal.

[0039] Example 5

[0040] The preparation method of the zinc-mercury-gallium-selenium far-infrared nonlinear optical crystal is carried out according to the following steps:

[0041] a. In a glove box filled with inert gas and sealed container containing 0.08 ppm of both water and oxygen, ZnSe, HgSe, and Ga2Se3 are weighed and mixed thoroughly in a mass ratio of 4:5:5. The mixture is then placed into a quartz glass tube, and the tube is placed under a vacuum of 10... -5 -10 -3 After vacuuming, Pa is sealed, and the inert gas is argon.

[0042] b. Place the sealed quartz tube from step a into a high-temperature furnace and raise it to 1100℃ at a heating rate of 38℃ / h, and hold it at that temperature for 100h.

[0043] c. Then cool to room temperature at a rate of 3℃ / h to obtain zinc mercury gallium selenide (Zn) with dimensions of 0.5mm × 0.5mm × 0.3mm. 0.8 Hg 0.2 Ga2Se4 mid-to-far infrared nonlinear optical crystal.

[0044] Example 6

[0045] The preparation method of the zinc-mercury-gallium-selenium far-infrared nonlinear optical crystal is carried out according to the following steps:

[0046] a. In a sealed glove box filled with inert gas and containing 0.1 ppm of both water and oxygen, ZnSe, HgSe, and Ga2Se3 were weighed and mixed thoroughly in a mass ratio of 4:5:5. The mixture was then placed into a quartz glass tube, and the tube was placed under a vacuum of 10... -5 -10 -3 After vacuuming, Pa is sealed, and the inert gas is argon.

[0047] b. Place the sealed quartz tube from step a into a high-temperature furnace and raise the temperature to 1150℃ at a rate of 40℃ / h, and hold for 100h.

[0048] c. Then cool to room temperature at a rate of 5℃ / h to obtain zinc mercury gallium selenide (Zn) with dimensions of 0.3mm × 0.5mm × 0.4mm. 0.8 Hg 0.2 Ga2Se4 mid-to-far infrared nonlinear optical crystal.

[0049] Example 7

[0050] The preparation method of the zinc-mercury-gallium-selenium far-infrared nonlinear optical crystal is carried out according to the following steps:

[0051] a. In a glove box filled with inert gas and sealed container containing 0.01 ppm of both water and oxygen, ZnSe, HgSe, and Ga2Se3 are weighed and mixed thoroughly in a mass ratio of 4:5:5. The mixture is then placed into a quartz glass tube, and the tube is placed under a vacuum of 10... -5 -10 -3 After vacuuming, Pa is sealed, and the inert gas is argon.

[0052] b. Place the sealed quartz tube from step a into a high-temperature furnace and raise the temperature to 1150℃ at a rate of 40℃ / h, and hold for 100h.

[0053] c. Then cool to room temperature at a rate of 5℃ / h to obtain zinc mercury gallium selenide (Zn) with dimensions of 0.4mm × 0.5mm × 0.6mm. 0.8 Hg 0.2 Ga2Se4 mid-to-far infrared nonlinear optical crystal.

[0054] Example 8

[0055] The preparation method of the zinc-mercury-gallium-selenium far-infrared nonlinear optical crystal is carried out according to the following steps:

[0056] a. In a sealed glove box filled with inert gas and containing 0.1 ppm of both water and oxygen, ZnSe, HgSe, and Ga2Se3 were weighed and mixed thoroughly in a mass ratio of 4:5:5. The mixture was then placed into a quartz glass tube, and the tube was placed under a vacuum of 10... -5 -10 -3 After vacuuming, Pa is sealed, and the inert gas is argon.

[0057] b. Place the sealed quartz tube from step a into a high-temperature furnace and raise the temperature to 1000℃ at a rate of 30℃ / h, and hold for 100h.

[0058] c. Then cool to room temperature at a rate of 4℃ / h to obtain zinc mercury gallium selenide (Zn) with dimensions of 0.5mm × 0.2mm × 0.4mm. 0.8 Hg 0.2 Ga2Se4 mid-to-far infrared nonlinear optical crystal.

[0059] Example 9

[0060] The preparation method of the zinc-mercury-gallium-selenium far-infrared nonlinear optical crystal is carried out according to the following steps:

[0061] a. In a glove box filled with inert gas and sealed container containing 0.05 ppm of both water and oxygen, ZnSe, HgSe, and Ga2Se3 are weighed and mixed thoroughly in a mass ratio of 4:5:5. The mixture is then placed into a quartz glass tube, and the tube is placed under a vacuum of 10... -5 -10 -3 After vacuuming, Pa is sealed, and the inert gas is argon.

[0062] b. Place the sealed quartz tube from step a into a high-temperature furnace and raise the temperature to 1100℃ at a rate of 35℃ / h, and hold for 100h.

[0063] c. Then cool to room temperature at a rate of 4℃ / h to obtain zinc mercury gallium selenide (Zn) with dimensions of 0.5mm × 0.5mm × 0.2mm. 0.8 Hg 0.2 Ga2Se4 mid-to-far infrared nonlinear optical crystal.

[0064] Example 10

[0065] Take any one of the zinc-mercury-gallium-selenium mid-far-infrared nonlinear optical crystals obtained in Examples 2-9, and apply it according to the attached... Figure 4As shown, when placed at position 3, at room temperature, using the 2090nm output of a Q-switched Ho:Tm:Cr:YAG laser as the light source, a significant 1045nm frequency-doubled light output was observed, with an output intensity four times that of AgGaS2 under the same conditions. Figure 4 As shown, an infrared beam with a wavelength of 2090nm emitted by a Q-switched Ho:Tm:Cr:YAG laser 1 is incident on a zinc mercury gallium selenide nonlinear optical crystal through a full-focus lens 2, generating frequency-doubled light with a wavelength of 1045nm. The outgoing beam 4 contains infrared light with a wavelength of 2090nm and light with a wavelength of 1045nm. After being filtered by a filter 5, the frequency-doubled light with a wavelength of 1045nm is obtained.

Claims

1. A compound zinc mercury gallium selenide, characterized in that... The chemical formula of this compound is Zn. 0.8 Hg 0.2 Ga₂Se₄, with a molecular weight of 547.71, is a non-centrosymmetric single crystal with a tetragonal crystal system and space group [space group missing]. I -4, cell parameters a = 5.5627(6)Å, b = 5.5627(6)Å, c = 10.881(2)Å, α = β = γ = 90°, Z = 2, unit cell volume V = 336.69(8)Å 3 .

2. A zinc-mercury-gallium-selenium mid-far-infrared nonlinear optical crystal, characterized in that... The chemical formula of this crystal is Zn. 0.8 Hg 0.2 Ga₂Se₄, with a molecular weight of 547.71, is a non-centrosymmetric single crystal with a tetragonal crystal system and space group [space group missing]. I -4, cell parameters a = 5.5627(6)Å, b = 5.5627(6)Å, c = 10.881(2)Å, α = β = γ = 90°, Z = 2, unit cell volume V = 336.69(8)Å 3 .

3. The method for preparing the zinc-mercury-gallium-selenium mid-far-infrared nonlinear optical crystal as described in claim 2, characterized in that, It is manufactured using a vacuum sealing method, and the specific operation is carried out according to the following steps: a. In a sealed glove box filled with inert gas and containing 0.01-0.1 ppm of both water and oxygen, ZnSe, HgSe, and Ga2Se3 are weighed and mixed thoroughly in a mass ratio of 4:5:

5. The mixture is then placed into a quartz glass tube, and the tube is placed under a vacuum of 10... -5 -10 -3 After vacuuming, Pa is sealed, and the inert gas is argon. b. Place the sealed quartz tube from step a into a high-temperature furnace and raise the temperature to 1000-1150℃ at a rate of 30-40℃ / h, and keep it at that temperature for 100h. c. Then cool to room temperature at a rate of 3-5℃ / h to obtain zinc mercury gallium selenide (Zn). 0.8 Hg 0.2 Ga2Se4 mid-to-far infrared nonlinear optical crystal.

4. The method for preparing the zinc-mercury-gallium-selenium far-infrared nonlinear optical crystal as described in claim 3, characterized in that... In step c, the compound is cooled at a rate of 4 °C / h.

5. The use of the zinc-mercury-gallium-selenium far-infrared nonlinear optical crystal as described in claim 3 in the preparation of infrared band laser frequency conversion crystals, infrared communication devices, or infrared laser guidance devices.

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