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

Abstract

The invention provides a compound zinc-mercury-gallium-selenium and a far-infrared nonlinear optical crystal in zinc-mercury-gallium-selenium as well as a preparation method and application thereof. The chemical formula of the compound is Zn0. 8Hg0. 2Ga2Se4, the molecular weight of the compound is 547.71, the chemical formula of the crystal is Zn0. 8Hg0. 2Ga2Se4, the molecular weight of the crystal is 547.71, the crystal is a tetragonal system, the space group is a non-centrosymmetric space group I-4, and the cell parameters are as follows: a = 5.5627 (6), b = 5.5627 (6), c = 10.881 (2), alpha = beta = gamma = 90 degrees, Z = 2 and unit cell volume V = 336.69 (8) 3. Preparing a powder pure sample and a single crystal by adopting a solid-phase reaction under a vacuum condition; a pure sample XRD (X-Ray Diffraction) diagram of the zinc-mercury-gallium-selenium infrared nonlinear optical crystal is matched with a theoretical value; an ultraviolet-visible diffuse reflection spectrum is used for measuring that the band gap of the crystal is 2.3 eV, and the ultraviolet cut-off edge is 489 nm; under the irradiation of laser with the wavelength of 2090 nm, the frequency doubling effect of Zn < 0.8 > Hg < 0.2 > Ga < 2 > Se with the granularity of 0.105-0.15 [mu] m is 4 times that of commercialized sulfur gallium silver (AgGaS2).

Description

Technical Field

[0001] The present invention belongs to the field of infrared nonlinear optical crystal materials, and particularly relates to a zinc mercury gallium selenide and a mid- and far-infrared nonlinear optical crystal thereof, a preparation method and an application Background Art

[0002] Nonlinear optical crystal materials can be classified into three categories according to the range of their transmission bands: 1. Nonlinear optical materials in the ultraviolet and deep ultraviolet bands; 2. Nonlinear optical materials in the visible and near-infrared bands; 3. Infrared and mid- and far-infrared nonlinear optical materials. The work of the present invention belongs to the visible and mid- and far-infrared nonlinear optical materials. The nonlinear optical crystal materials in this band have a wide range of uses, such as applications in laser frequency converters, infrared lidars, laser communications, infrared filter devices, optoelectronic countermeasures, etc

[0003] So far, the generation of 3-20μm solid-state mid- and far-infrared band lasers is mainly based on the nonlinear optical principle and the infrared nonlinear optical crystal frequency conversion technology. In the infrared nonlinear optical crystal market, common infrared nonlinear optical crystals mainly include AgGaS2, AgGaSe2, ZnGeP2, etc. Although these crystals have been used in high-tech fields of civilian production and life and military equipment, these crystal materials also have their own disadvantages and cannot meet the ideal requirements of people in terms of comprehensive performance. With the development of technology and the improvement of requirements, the demand for infrared nonlinear crystals with more excellent performance is more urgent. Therefore, the exploration of new mid- and far-infrared nonlinear crystals is of great strategic significance in both civilian high-tech industries and the improvement of military equipment, and the synthesis and growth of crystal materials is a huge challenge in this direction Summary of the Invention

[0004] The purpose of the present invention is to provide a compound zinc mercury gallium selenide and a mid- and far-infrared nonlinear optical crystal thereof, a preparation method and an application. The chemical formula of the compound is Zn 0.8 Hg 0.2 Ga2Se4, with a molecular weight of 547.71. The chemical formula of the crystal is Zn 0.8 Hg 0.2 Ga2Se4, with a molecular weight of 547.71, belonging to the tetragonal system, and the space group is the non-centrosymmetric space group I-4. The unit cell parameters α = β = γ = 90°, Z = 2, and the unit cell volume The preparation method includes a solid-phase reaction of zinc selenide, mercury selenide, and gallium selenide under vacuum conditions; the powder XRD pattern of the zinc mercury gallium selenide and the mid- and far-infrared nonlinear optical crystal thereof in the present invention is consistent with the theoretical value; under the irradiation of a 2090nm laser, the particle size of Zn 0.8 Hg0.2 The frequency doubling effect of Ga2Se4 is four times that of commercialized AgGaS2.

[0005] A zinc mercury gallium selenium compound according to the present invention, the chemical formula of the compound is Zn 0.8 Hg 0.2 Ga2Se4, with a molecular weight of 547.71, is a non-centrosymmetric single crystal, the crystal system is tetragonal, the space group is I-4, and the unit cell parameters α = β = γ = 90°, Z = 2, and the unit cell volume

[0006] A zinc mercury gallium selenium mid-infrared nonlinear optical crystal, the chemical formula of the crystal is Zn 0.8 Hg 0.2 Ga2Se4, with a molecular weight of 547.71, is a non-centrosymmetric single crystal, the crystal system is tetragonal, the space group is I-4, and the unit cell parameters α = β = γ = 90°, Z = 2, and the unit cell volume

[0007] The preparation method of the zinc mercury gallium selenium mid-infrared nonlinear optical crystal is made by the vacuum sealed tube method, and the specific operation is carried out according to the following steps:

[0008] a. Weigh ZnSe, HgSe, and Ga2Se3 in a mass ratio of 4:5:5 and mix them evenly in a glove box filled with inert gas in a closed container with a water content and an oxygen content of 0.01 - 0.1 ppm, then load them into a quartz glass tube. After evacuating the quartz tube to a vacuum degree of 10 -5 -10 -3 Pa and sealing it, and the inert gas is argon;

[0009] b. Place the sealed quartz tube in step a in a high-temperature furnace, and raise the temperature to 1000 - 1150 °C at a heating rate of 30 - 40 °C / h and keep it warm for 100 h;

[0010] c. Then cool it down to room temperature at a rate of 3 - 5 °C / h to obtain the zinc mercury gallium selenium Zn 0.8 Hg 0.2 Ga2Se4 mid-infrared nonlinear optical crystal.

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

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

[0013] In the zinc-mercury-gallium-selenium mid-infrared nonlinear optical crystal of the present invention, in the crystal structure, the valence states of Zn atoms, Hg atoms, Ga atoms, and Se atoms are +2, +2, +3, and -2 respectively. Both Zn / Hg and Ga atoms form tetrahedral structures with four adjacent Se atoms. The two tetrahedrons stack to form a diamond-like structure through the common fixed-point selenium atoms, and the zinc-mercury-gallium-selenium compound is zinc-mercury-gallium-selenium single crystal particles. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 It is a comparison chart 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 Zn of the present invention 0.8 Hg 0.2 UV-visible diffuse reflection diagram of Ga2Se4;

[0016] Figure 3 For the compound Zn of the present invention 0.8 Hg 0.2 Structure diagram of the single crystal of Ga2Se4;

[0017] Figure 4 For the compound Zn of the present invention 0.8 Hg 0.2 Crystal photograph diagram of Ga2Se4;

[0018] Figure 5 For Zn of the present invention 0.8 Hg 0.2 Working principle diagram of the nonlinear optical device made of the Ga2Se4 crystal, where 1 is a laser, 2 is the emitted light beam, 3 is the Ga2Se4 crystal of Zn 0.8 Hg 0.2 Ga2Se4 crystal, 4 is the outgoing light beam, and 5 is a filter. DETAILED DESCRIPTION OF THE INVENTION

[0019] For the compound zinc-mercury-gallium-selenium and the zinc-mercury-gallium-selenium mid-infrared nonlinear optical crystal and the preparation method and application of the present invention, the preparation of the obtained zinc-mercury-gallium-selenium polycrystalline powder and single crystal both adopt the high-temperature solid-phase reaction method in a closed system, but their process parameters are significantly different. During the synthesis of the polycrystalline powder, the constant-temperature sintering temperature is set at 950 °C, the heating rate is 92 °C / h, and the cooling rate is 38 °C / h; while the single crystal growth needs to be carried out in the temperature range of 1000 - 1100 °C, the heating rate is controlled at 30 - 40 °C / h, and a precise cooling process of 4 - 5 °C / h is implemented. The present invention is described in detail through examples. But it 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 in a closed container with both water content and oxygen content of 0.1 ppm, weigh Zn, HgSe, Ga2Se3 and Se according to the molar ratio of Zn:HgSe:Ga2Se3:Se of 4:1:5:4, mix them evenly, then load them into a quartz glass tube, evacuate the quartz tube and seal it;

[0023] b. Place the sealed quartz tube in step a in a high-temperature furnace, let the temperature reach 950 °C in 10 hours, keep it warm for 24 hours, and then quickly cool it to room temperature in 24 hours to obtain orange polycrystalline powder. Conduct X-ray powder diffraction on the prepared polycrystalline phase, and the results are shown in Figure 1 , it can be seen from the figure that the experimental values are in good agreement with the theoretical values, indicating that the obtained powder sample is a pure phase.

[0024] Example 2

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

[0026] a. In a glove box filled with inert gas in a closed container with both water content and oxygen content of 0.01 ppm, weigh ZnSe, HgSe, Ga2Se3 according to the mass ratio of 4:5:5, mix them evenly, then load them into a quartz glass tube, and evacuate the quartz tube to a vacuum of 10 -5 -10 -3 Pa and seal it. The inert gas is argon;

[0027] b. Place the sealed quartz tube in step a in a high-temperature furnace, and raise the temperature to 1000 °C at a heating rate of 30 °C / h and keep it warm for 100 h;

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

[0029] Example 3

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

[0031] a. In a glove box filled with inert gas in a closed container with both water content and oxygen content of 0.03 ppm, weigh ZnSe, HgSe, Ga2Se3 according to the mass ratio of 4:5:5, mix them evenly, then load them into a quartz glass tube, and evacuate the quartz tube to a vacuum of 10 -5 -10 -3 Pa and seal it. The inert gas is argon;

[0032] b. Place the sealed quartz tube in step a in a high-temperature furnace and heat it to 1050 °C at a heating rate of 32 °C / h, and keep it at this temperature for 100 h;

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

[0034] Example 4

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

[0036] a. Weigh ZnSe, HgSe, and Ga2Se3 in a glove box filled with inert gas in a closed container with both water content and oxygen content of 0.05 ppm according to a mass ratio of 4:5:5, mix them evenly, then load them into a quartz glass tube. After evacuating the quartz tube to a vacuum of 10 -5 -10 -3 Pa and sealing it, and the inert gas is argon;

[0037] b. Place the sealed quartz tube in step a in a high-temperature furnace and heat it to 1080 °C at a heating rate of 35 °C / h, and keep it at this temperature for 100 h;

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

[0039] Example 5

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

[0041] a. Weigh ZnSe, HgSe, and Ga2Se3 in a glove box filled with inert gas in a closed container with both water content and oxygen content of 0.08 ppm according to a mass ratio of 4:5:5, mix them evenly, then load them into a quartz glass tube. After evacuating the quartz tube to a vacuum of 10 -5 -10 -3 Pa and sealing it, and the inert gas is argon;

[0042] b. Place the sealed quartz tube in step a in a high-temperature furnace and heat it to 1100 °C at a heating rate of 38 °C / h, and keep it at this temperature for 100 h;

[0043] c. Then cool it down to room temperature at a rate of 3 °C / h to obtain a ZnHgGa₂Se₄ mid-infrared nonlinear optical crystal with dimensions of 0.5 mm × 0.5 mm × 0.3 mm. 0.8 Hg 0.2 mid-infrared nonlinear optical crystal

[0044] Example 6

[0045] The preparation method of the ZnHgGa₂Se₄ mid-infrared nonlinear optical crystal is carried out according to the following steps:

[0046] a. Weigh ZnSe, HgSe, and Ga₂Se₃ in a mass ratio of 4:5:5 and mix them evenly in a glove box filled with inert gas in a closed container with both water content and oxygen content of 0.1 ppm. Then load them into a quartz glass tube. After evacuating the quartz tube to a vacuum of 10 -5 -10 -3 Pa and sealing it, where the inert gas is argon;

[0047] b. Place the sealed quartz tube in step a in a high-temperature furnace and heat it to 1150 °C at a heating rate of 40 °C / h, and keep it at this temperature for 100 h;

[0048] c. Then cool it down to room temperature at a rate of 5 °C / h to obtain a ZnHgGa₂Se₄ mid-infrared nonlinear optical crystal with dimensions of 0.3 mm × 0.5 mm × 0.4 mm. 0.8 Hg 0.2 mid-infrared nonlinear optical crystal

[0049] Example 7

[0050] The preparation method of the ZnHgGa₂Se₄ mid-infrared nonlinear optical crystal is carried out according to the following steps:

[0051] a. Weigh ZnSe, HgSe, and Ga₂Se₃ in a mass ratio of 4:5:5 and mix them evenly in a glove box filled with inert gas in a closed container with both water content and oxygen content of 0.01 ppm. Then load them into a quartz glass tube. After evacuating the quartz tube to a vacuum of 10 -5 -10 -3 Pa and sealing it, where the inert gas is argon;

[0052] b. Place the sealed quartz tube in step a in a high-temperature furnace and heat it to 1150 °C at a heating rate of 40 °C / h, and keep it at this temperature for 100 h;

[0053] c. Then cool it down to room temperature at a rate of 5 °C / h to obtain a ZnHgGa₂Se₄ mid-infrared nonlinear optical crystal with dimensions of 0.4 mm × 0.5 mm × 0.6 mm. 0.8 Hg 0.2 mid-infrared nonlinear optical crystal

[0054] Example 8

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

[0056] a. In a glove box filled with inert gas with both water content and oxygen content of 0.1 ppm, weigh ZnSe, HgSe, and Ga2Se3 according to a mass ratio of 4:5:5, mix them evenly, then load them into a quartz glass tube. After evacuating the quartz tube to a vacuum of 10 -5 -10 -3 Pa and sealing it, the inert gas is argon;

[0057] b. Place the sealed quartz tube in step a in a high-temperature furnace, and raise the temperature to 1000 °C at a heating rate of 30 °C / h, and keep it warm for 100 h;

[0058] c. Then cool it down to room temperature at a rate of 4 °C / h to obtain a zinc-mercury-gallium-selenium Zn 0.8 Hg 0.2 Ga2Se4 mid-infrared nonlinear optical crystal with dimensions of 0.5 mm × 0.2 mm × 0.4 mm.

[0059] Example 9

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

[0061] a. In a glove box filled with inert gas with both water content and oxygen content of 0.05 ppm, weigh ZnSe, HgSe, and Ga2Se3 according to a mass ratio of 4:5:5, mix them evenly, then load them into a quartz glass tube. After evacuating the quartz tube to a vacuum of 10 -5 -10 -3 Pa and sealing it, the inert gas is argon;

[0062] b. Place the sealed quartz tube in step a in a high-temperature furnace, and raise the temperature to 1100 °C at a heating rate of 35 °C / h, and keep it warm for 100 h;

[0063] c. Then cool it down to room temperature at a rate of 4 °C / h to obtain a zinc-mercury-gallium-selenium Zn 0.8 Hg 0.2 Ga2Se4 mid-infrared nonlinear optical crystal with dimensions of 0.5 mm × 0.5 mm × 0.2 mm.

[0064] Example 10

[0065] Take any one of the zinc-mercury-gallium-selenium mid-infrared nonlinear optical crystals obtained in Examples 2-9, according to the attached Figure 4Placed at the position of 3, at room temperature, using the 2090 nm output of a Q-switched Ho:Tm:Cr:YAG laser as the light source, an obvious second harmonic generation (SHG) light output of 1045 nm was observed, and the output intensity was 4 times that of AgGaS2 under the same conditions. Figure 4 As shown, an infrared beam with a wavelength of 2090 nm emitted by a Q-switched Ho:Tm:Cr:YAG laser 1 is incident on a zinc mercury gallium selenide nonlinear optical crystal through a total focusing lens 2, generating a second harmonic generation (SHG) light with a wavelength of 1045 nm. The output beam 4 contains infrared light with a wavelength of 2090 nm and light with a wavelength of 1045 nm. After being filtered by a filter 5, the second harmonic generation (SHG) light with a wavelength of 1045 nm 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. It is a non-centrosymmetric single crystal, belonging to the tetragonal crystal system, and the space group is I -4. The unit cell parameters are a = 5.5627(6) Å, b = 5.5627(6) Å, c = 10.881(2) Å, α = β = γ = 90°, Z = 2, and the unit cell volume V = 336.69(8) Å 3 .

2. A zinc mercury gallium selenium mid-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. Its crystal system is tetragonal, and the space group is I -4. The unit cell parameters are a = 5.5627(6) Å, b = 5.5627(6) Å, c = 10.881(2) Å, α = β = γ = 90°, Z = 2, and the unit cell volume V = 336.69(8) Å 3 .

3. The preparation method of the zinc mercury gallium selenium mid-infrared nonlinear optical crystal according to claim 3, characterized in that, It is made by the vacuum sealing tube method, and the specific operation is carried out according to the following steps: a. In a glove box filled with inert gas in a closed container with a water content and an oxygen content both of 0.01 - 0.1 ppm, weigh ZnSe, HgSe, and Ga2Se3 according to a mass ratio of 4:5:5 and mix them evenly. Then load them into a quartz glass tube. After evacuating the quartz tube to a vacuum of 10 -5 -10 -3 Pa and sealing it, the inert gas is argon; b. Place the quartz tube sealed in step a in a high-temperature furnace, and raise the temperature to 1000 - 1150 °C at a heating rate of 30 - 40 °C / h, and keep the temperature for 100 h; c. Then cool it to room temperature at a rate of 3 - 5 °C / h to obtain a mid-infrared nonlinear optical crystal of zinc mercury gallium selenide Zn 0.8 Hg 0.2 Ga2Se4.

4. The preparation method of the zinc mercury gallium selenium mid-infrared nonlinear optical crystal according to claim 4, characterized in that In step c, the cooling rate of the compound is 4 °C / h.

5. Use of the zinc mercury gallium selenium mid-infrared nonlinear optical crystal as described in claim 3 in the preparation of an infrared band laser frequency conversion crystal, an infrared communication device or an infrared laser guidance device.

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