Selenium phosphorus zinc halide compound, nonlinear optical crystal material thereof, and preparation method and application of nonlinear optical crystal material

Abstract

The invention discloses a selenium phosphorus zinc halide compound, a nonlinear optical crystal thereof, and a preparation method and application of the nonlinear optical crystal. The compound does not have a symmetric center and is crystallized in a trigonal system, the space group is R3m, and the unit cell parameters of Zn0. 8P0. 2Se0. 2Br0. 6 are as follows: # imgabs0 # alpha = beta = 90 degrees, gamma = 120 degrees and Z = 3; and the unit cell parameters of the Zn0. 8P0. 2Se0. 2I0. 6 are as follows: # imgabs1 # alpha = beta = 90 degrees, gamma = 120 degrees, and Z = 3. The bromine-selenium-phosphorus-zinc and iodine-selenium-phosphorus-zinc nonlinear optical crystal has the advantages of large nonlinear optical effect, relatively large band gap value, wide infrared transmission range, good mechanical property and the like, and can be widely applied to various nonlinear optical fields and middle infrared bands.

Description

Technical Field

[0001] The present invention belongs to the field of infrared nonlinear optical crystals and relates to a halogenated selenium-phosphorus-zinc compound, a nonlinear optical crystal material thereof, a preparation method and uses thereof, and specifically relates to a bromine-selenium-phosphorus-zinc or iodine-selenium-phosphorus-zinc compound and a bromine-selenium-phosphorus-zinc or iodine-selenium-phosphorus-zinc nonlinear optical crystal, a preparation method and uses thereof. Background Art

[0002] Mid-infrared lasers (2.5-25 μm), especially long-wavelength infrared tunable lasers in the 8-14 μm range, have important applications in many areas, such as laser guidance, optoelectronic countermeasures, infrared remote sensing, medical diagnostics, and environmental monitoring. Currently, commercial infrared nonlinear optical crystal materials used in long-wavelength infrared lasers are primarily AgGaS2, AgGaSe2, and ZnGeP2. However, these commercial materials have been found to have inherent limitations in their applications, including the low laser damage threshold of AgGaS2 crystals, non-phase-matching behavior of AgGaSe2 crystals, and two-photon absorption of ZnGeP2 crystals. These issues hinder their ability to meet the growing demands of various applications. Therefore, the search for novel infrared nonlinear optical crystals with large frequency-harmonic effects (>1×AGS), wide band gaps (Eg>2.33 eV to avoid two-photon absorption of 1064 nm lasers), and moderate birefringence (Δn=0.03-0.1 to support phase matching) is of great significance. Summary of the Invention

[0003] In order to improve the above technical problems, the present invention provides a selenium halogenide phosphorus zinc compound, the chemical formula of which is Zn 0.8 P 0.2 Se 0.2 X 0.6 , X is selected from F, Cl, Br or I, preferably Br or I.

[0004] According to an embodiment of the present invention, the halogenated selenium phosphorus zinc compound is bromoselenium phosphorus zinc (Zn 0.8 P 0.2 Se 0.2 Br 0.6 ) or iodine, selenium, phosphorus and zinc (Zn 0.8 P 0.2 Se 0.2 I 0.6 ).

[0005] According to an embodiment of the present invention, the selenium phosphorus zinc halide compound is prepared by mixing raw materials including a Zn source, a P source, a Se source and an X source and calcining them at a high temperature.

[0006] The present invention also provides a preparation method of the selenium halogenide phosphorus zinc compound, which comprises: mixing a Zn source, a P source, a Se source and an X source, and calcining the mixture at a high temperature to obtain the selenium halogenide phosphorus zinc compound.

[0007] According to an embodiment of the present invention, the preparation method further comprises grinding the mixed substances.

[0008] According to an embodiment of the present invention, the molar ratio of the element Zn in the Zn source, the element P in the P source, the element Se in the Se source, and the element X in the X source is 1-8.5:1:1:3-12, preferably 1-5:1:1:3-4 or 7.5-8.5:1:1:8-12.

[0009] In some embodiments, the molar ratio of element Zn in the Zn source, element P in the P source, element Se in the Se source, and element X in the X source is 1-5:1:1:3-4, for example, 4:1:1:3, 4.5:1:1:3, 5:1:1:3, 4:1:1:3.5, 4:1:1:4, 5:1:1:4, 5:1:1:3.5, or 5:1:1:4.

[0010] In some embodiments, the molar ratio of element Zn in the Zn source, element P in the P source, element Se in the Se source, and element X in the X source is 7.5-8.5:1:1:8-12, for example, 8.5:1:1:12, 8.5:1:1:8, 8.5:1:1:10, 7.5:1:1:8, 7.5:1:1:10, 7.5:1:1:12, 8:1:1:8, 8:1:1:10, or 8:1:1:12.

[0011] According to an embodiment of the present invention, the Zn source is selected from at least one of Zn element, Zn3P2, ZnSe, ZnBr2 and ZnI2.

[0012] According to an embodiment of the present invention, the P source is selected from at least one of P element and Zn3P2.

[0013] According to an embodiment of the present invention, the Se source is selected from at least one of a single substance of Se and ZnSe.

[0014] According to an embodiment of the present invention, the X source is provided by a compound containing element X. For example, it is selected from ZnBr2 and ZnI2.

[0015] According to an embodiment of the present invention, the high-temperature calcination temperature is 550°C-650°C, exemplified by 550°C, 560°C, 570°C, 580°C, 590°C, 600°C, or 650°C; the calcination time is 48 hours-120 hours, exemplified by 48 hours, 50 hours, 60 hours, 72 hours, 80 hours, 96 hours, 100 hours, or 120 hours. Preferably, the heating rate is 10°C / h-30°C / h, preferably 10°C / h-25°C / h, exemplified by 10°C / h, 15°C / h, 20°C / h, 25°C / h, or 30°C / h.

[0016] According to an embodiment of the present invention, the preparation method further comprises cooling the product after high-temperature calcination. Preferably, the cooling is to cool the product to 400°C to 300°C at a rate of 1°C / h to 3°C / h (e.g., 2°C / h), and then to room temperature at a rate of 4°C / h to 6°C / h (e.g., 5°C / h).

[0017] According to an exemplary embodiment of the present invention, the preparation method of the bromine-selenium-phosphorus-zinc or iodine-selenium-phosphorus-zinc compound comprises:

[0018] The Zn source, P source, Se source and Br source or I source are mixed, ground, and calcined at high temperature (high temperature gas phase transport) to obtain the bromine-selenium-phosphorus-zinc / iodine-selenium-phosphorus-zinc compound.

[0019] In some embodiments, the high-temperature calcination is performed in a horizontal dual-zone tube furnace.

[0020] According to an embodiment of the present invention, the high temperature gas phase transport is carried out at a vacuum degree of 10 -5 -10 -1 For example, the raw materials (such as Zn source, P source, Se source and Br source / I source) are mixed and ground and then placed in a quartz tube, which is then evacuated to 10 -5 -10 -3 After Pa is sealed using a hydrogen-oxygen flame, high-temperature gas phase transport growth is carried out using a horizontal double-temperature zone tubular furnace.

[0021] In some embodiments, during high-temperature gas-phase transport, the high-temperature end (i.e., the evaporation end) of the horizontal double-temperature-zone tubular furnace is heated to 600-650°C at a rate of 10°C / h-25°C / h, and the low-temperature end (i.e., the crystallization end) of the horizontal double-temperature-zone tubular furnace is heated to 550-580°C at a rate of 15°C / h-25°C / h, and constant-temperature calcination is carried out for 48 hours to 120 hours.

[0022] In some embodiments, after calcination, the temperature is lowered, for example, by lowering the temperature at the high temperature end to 300°C-350°C at a rate of 1°C / h-3°C / h, lowering the temperature at the low temperature end to 250°C-280°C at a rate of 1°C / h-3°C / h, and then lowering the temperature to room temperature at a rate of 4°C / h-6°C / h (e.g., 5°C / h).

[0023] The present invention also provides a selenium halogenide zinc phosphorus crystal, the chemical formula of which is Zn 0.8 P 0.2 Se 0.2 X 0.6 , X is selected from F, Cl, Br or I, preferably Br or I.

[0024] According to an embodiment of the present invention, the selenium phosphine zinc halide crystal is bromine selenium phosphine zinc (Zn 0.8 P 0.2 Se 0.2 Br 0.6 ) or iodine, selenium, phosphorus and zinc (Zn 0.8 P 0.2 Se 0.2 I 0.6 ).

[0025] According to an embodiment of the present invention, the crystal has substantially Figure 1 The molecular structure is shown.

[0026] According to an embodiment of the present invention, the crystal material belongs to the trigonal system and the space group is R3m. According to an embodiment of the present invention, the unit cell parameters of the bromine selenium phosphorus zinc crystal are: α=β=90°, γ=120°, Z=3,

[0027] In some embodiments, the unit cell parameters of the bromo-selenium-phosphorus-zinc crystals are: α=β=90°, γ=120°, Z=3,

[0028] According to an embodiment of the present invention, the unit cell parameters of the iodine-selenium-phosphorus-zinc crystal are: α=β=90°, γ=120°, Z=3,

[0029] In some embodiments, the unit cell parameters of the iodine-selenium-phosphorus-zinc crystal are: α=β=90°, γ=120°, Z=3,

[0030] According to an embodiment of the present invention, the selenium halide phosphorus zinc crystal is a nonlinear optical crystal.

[0031] The present invention also provides a preparation method of the selenium halogenide phosphorus zinc crystal. The preparation method comprises: mixing a Zn source, a P source, a Se source and an X source, and calcining the mixture at a high temperature to obtain the selenium halogenide phosphorus zinc crystal.

[0032] According to an embodiment of the present invention, the preparation method further comprises grinding the mixed substances.

[0033] According to an embodiment of the present invention, the molar ratio of the element Zn in the Zn source, the element P in the P source, the element Se in the Se source, and the element X in the X source is 1-8.5:1:1:3-12, preferably 1-5:1:1:3-4 or 7.5-8.5:1:1:8-12.

[0034] In some embodiments, the molar ratio of element Zn in the Zn source, element P in the P source, element Se in the Se source, and element X in the X source is 1-5:1:1:3-4, for example, 4:1:1:3, 4.5:1:1:3, 5:1:1:3, 4:1:1:3.5, 4:1:1:4, 5:1:1:4, 5:1:1:3.5, or 5:1:1:4.

[0035] In some embodiments, the molar ratio of element Zn in the Zn source, element P in the P source, element Se in the Se source, and element X in the X source is 7.5-8.5:1:1:8-12, for example, 8.5:1:1:12, 8.5:1:1:8, 8.5:1:1:10, 7.5:1:1:8, 7.5:1:1:10, 7.5:1:1:12, 8:1:1:8, 8:1:1:10, or 8:1:1:12.

[0036] According to an embodiment of the present invention, the Zn source is selected from at least one of Zn element, Zn3P2, ZnSe, ZnBr2 and ZnI2.

[0037] According to an embodiment of the present invention, the P source is selected from at least one of P element and Zn3P2.

[0038] According to an embodiment of the present invention, the Se source is selected from at least one of a single substance of Se and ZnSe.

[0039] According to an embodiment of the present invention, the X source is provided by a compound containing element X. For example, it is selected from at least one of ZnBr2 and ZnI2.

[0040] The inventors have found through a large number of experiments that the X source of the present invention can also act as a flux during the reaction process. By adding an excess of X source as a self-flux, the raw materials Zn3P2 and ZnSe with higher melting and boiling points are promoted to melt and participate in the crystallization reaction to obtain a pure phase of selenium halide phosphorus zinc crystals.

[0041] According to the embodiment of the present invention, the mixing and grinding can be performed by methods known in the art, which are not specifically limited in the present invention.

[0042] According to an embodiment of the present invention, high temperature calcination is carried out at a vacuum degree of 10 -5 -10 -1 Pa, preferably 10 -5 -10 - 3 For example, the raw materials (such as Zn source, P source, Se source and X source and self-solvent) are mixed and ground and then placed in a quartz tube, which is then evacuated to 10 -5 -10 -3 Pa, after being sealed with a hydrogen-oxygen flame, is calcined at high temperature in a muffle furnace.

[0043] According to an embodiment of the present invention, the high-temperature calcination temperature is 550°C-650°C, exemplified by 550°C, 600°C, 610°C, 620°C, 630°C, 640°C, or 650°C; the calcination time is 48 hours-120 hours, exemplified by 48 hours, 50 hours, 60 hours, 72 hours, 80 hours, 96 hours, 100 hours, or 120 hours. Preferably, the heating rate is 10°C / h-30°C / h, preferably 10°C / h-25°C / h, exemplified by 10°C / h, 15°C / h, 20°C / h, 25°C / h, or 30°C.

[0044] According to an embodiment of the present invention, the preparation method further comprises cooling the product after high-temperature calcination. Preferably, the cooling is performed at a rate of 1°C / h-3°C / h (e.g., 2°C / h) to 400°C-300°C, and then at a rate of 4°C / h-6°C / h (e.g., 5°C / h) to room temperature.

[0045] According to the embodiment of the present invention, in the preparation method, when an excess of X source is added as a flux, after cooling and opening the tube, the excess white ZnBr2 / ZnI2 blocks can be mixed with the cyan Zn 0.8 P 0.2 Se 0.2 Br 0.6 / Greenish-yellow Zn 0.8 P 0.2 Se 0.2 I 0.6 The crystals are separated mechanically.

[0046] According to an embodiment of the present invention, the preparation method of the bromine-selenium-phosphorus-zinc / iodine-selenium-phosphorus-zinc crystals comprises:

[0047] The Zn source, P source, Se source and Br source / I source are mixed, ground, and calcined at high temperature (high temperature gas phase transport) to obtain the bromine-selenium-phosphorus-zinc / iodine-selenium-phosphorus-zinc nonlinear optical crystal.

[0048] In some embodiments, the high-temperature calcination is performed in a horizontal dual-zone tube furnace.

[0049] According to an exemplary embodiment of the present invention, high temperature gas phase transport is carried out at a vacuum degree of 10 -5 -10 -1 For example, the raw materials (such as Zn source, P source, Se source and Br source / I source) are mixed and ground and then placed in a quartz tube, which is then evacuated to 10 -5 -10 -3 After Pa is sealed using a hydrogen-oxygen flame, high-temperature gas phase transport growth is carried out using a horizontal double-temperature zone tubular furnace.

[0050] In some embodiments, during high-temperature gas-phase transport, the high-temperature end (i.e., the evaporation end) of the horizontal double-temperature-zone tubular furnace is heated to 600-650°C at a rate of 10°C / h-25°C / h, and the low-temperature end (i.e., the crystallization end) of the horizontal double-temperature-zone tubular furnace is heated to 550-580°C at a rate of 15°C / h-25°C / h, and constant-temperature calcination is carried out for 48 hours to 120 hours.

[0051] In some embodiments, after calcination, the temperature is lowered, for example, by lowering the temperature at the high temperature end to 300°C-350°C at a rate of 1°C / h-3°C / h, lowering the temperature at the low temperature end to 250°C-280°C at a rate of 1°C / h-3°C / h, and then lowering the temperature to room temperature at a rate of 4°C / h-6°C / h (e.g., 5°C / h).

[0052] The present invention also provides the above-mentioned selenium phosphorus zinc halide compound and / or selenium phosphorus zinc halide crystal for use in the field of nonlinear optics or in the mid-infrared band, for example, in nonlinear optical devices.

[0053] The present invention also provides a nonlinear optical device, which comprises the above-mentioned selenium halide phosphorus zinc compound and / or selenium halide phosphorus zinc crystal.

[0054] According to an embodiment of the present invention, in the nonlinear optical device, at least one beam of incident electromagnetic radiation passes through at least one piece of the selenium halogenide phosphorus zinc compound and / or selenium halogenide phosphorus zinc crystal to generate at least one beam of output radiation with a frequency different from the incident electromagnetic radiation.

[0055] According to an embodiment of the present invention, the nonlinear optical device includes but is not limited to at least one of an infrared laser frequency conversion device, an infrared electro-optical device, an infrared communication device, an infrared laser guidance device and an infrared optoelectronic countermeasure system.

[0056] Beneficial effects of the present invention:

[0057] The bromine-selenium-phosphorus-zinc or iodine-selenium-phosphorus-zinc nonlinear optical crystal Zn of the present invention 0.8 P 0.2 Se 0.2 Br 0.6 、Zn 0.8 P 0.2 Se 0.2 I 0.6 It has the advantages of large nonlinear optical effect (the frequency-doubled output intensity is about 4.2 times and 5.0 times that of AgGaS2 under the same conditions), wide band gap value (2.90eV and 2.80eV), easy growth, high hardness, good mechanical properties, easy processing and preservation. It can be used in various nonlinear optical fields or in the mid-infrared band to prepare infrared laser frequency conversion devices, infrared electro-optical devices, infrared communication devices or infrared laser guidance devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0058] Figure 1 It is an iodine-selenium-phosphorus-zinc nonlinear optical crystal Zn 0.8 P 0.2 Se 0.2 I 0.6 Schematic diagram of the crystal structure; in which: Zn is tetracoordinated with P and Se atoms in the crystal structure, there are 20% cation vacancies in Zn, and P, Se, and I occupy anions at 20%, 20%, and 60%, respectively. It is a typical defective diamond-like structure. The two compounds are isomorphous. Zn is selected 0.8 P 0.2 Se 0.2 I 0.6 For example.

[0059] Figure 2 The bromine selenium phosphorus zinc compound obtained in Example 1, the iodine selenium phosphorus zinc compound obtained in Example 4 and the bromine selenium phosphorus zinc nonlinear optical crystal Zn obtained in Example 2 0.8 P 0.2 Se 0.2 Br 0.6 , the iodine-selenium-phosphorus-zinc nonlinear optical crystal Zn obtained in Example 5 0.8 P 0.2 Se 0.2 I 0.6 Comparison of X-ray powder diffraction and simulated X-ray diffraction.

[0060] Figure 3The nonlinear optical crystal ZnBrSePZN obtained in Example 3 0.8 P 0.2 Se 0.2 Br 0.6 , the iodine-selenium-phosphorus-zinc nonlinear optical crystal Zn obtained in Example 6 0.8 P 0.2 Se 0.2 I 0.6 UV transmittance diagram.

[0061] Figure 4 The nonlinear optical crystal Zn2 obtained in Example 2 is bromine selenium phosphorus zinc. 0.8 P 0.2 Se 0.2 Br 0.6 , the iodine-selenium-phosphorus-zinc nonlinear optical crystal Zn obtained in Example 5 0.8 P 0.2 Se 0.2 I 0.6 And the frequency doubling intensity and sample particle size curve of commercial AgGaS2 crystal. DETAILED DESCRIPTION

[0062] The technical solutions of the present invention will be described in further detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are encompassed within the scope of protection that the present invention is intended to protect.

[0063] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0064] Example 1

[0065] Preparation of Zn compounds by high temperature solid phase method 0.8 P 0.2 Se 0.2 Br 0.6 .

[0066] The chemical reaction equation is: 2.5Zn+P+Se+1.5ZnBr2=5Zn 0.8 P 0.2 Se 0.2 Br 0.6 , the specific steps are as follows:

[0067] The raw materials Zn, P, Se, and ZnBr2 were uniformly mixed and ground in a molar ratio of 2.5:1:1:1.5 to make the molar ratio of element Zn, element P, element Se, and element Br 4:1:1:3, and then placed in a quartz tube and evacuated to 10 -3Pa and melt-seal, place the sealed quartz tube in a program-controlled muffle furnace; heat to 550°C at a rate of 10°C / h, keep constant temperature for 96 hours, reduce to 300°C at a rate of 3°C / h, and then reduce to room temperature at a rate of 5°C / h, close the muffle furnace, and after cooling to room temperature, take out the quartz tube and cut it open to obtain a blue block of Zn 0.8 P 0.2 Se 0.2 Br 0.6 The compound has an X-ray powder diffraction pattern of Figure 2 As shown in the figure, the experimental XRD pattern is consistent with the theoretical simulation XRD pattern, indicating that Example 1 can obtain compound Zn 0.8 P 0.2 Se 0.2 Br 0.6 of pure phase.

[0068] Example 2

[0069] Preparation of Zn by self-solvent method 0.8 P 0.2 Se 0.2 Br 0.6 Infrared nonlinear optical crystals.

[0070] The chemical reaction equation is: 0.5Zn3P2+ZnSe+6ZnBr2=5Zn 0.8 P 0.2 Se 0.2 Br 0.6 +4.5ZnBr2, the specific steps are as follows:

[0071] The raw materials Zn3P2, ZnSe and ZnBr2 were uniformly mixed and ground in a molar ratio of 0.5:1:6 to make the molar ratio of Zn, P, Se and Br be 8.5:1:1:12, and then placed in a quartz tube and evacuated to 10 -3 Pa and melt seal, put the sealed quartz tube into a program-controlled muffle furnace: heat it to 600℃ at a rate of 10℃ / h, keep it constant for 96 hours, then reduce it to 300℃ at a rate of 3℃ / h, and then reduce it to room temperature at a rate of 5℃ / h. Close the muffle furnace, wait for it to cool to room temperature, take out the quartz tube, cut it open, and separate the excess white ZnBr2 blocks from the cyan Zn 0.8 P 0.2 Se 0.2 Br 0.6 The crystals are separated mechanically.

[0072] The test shows that the Zn prepared in this embodiment 0.8 P 0.2 Se 0.2 Br 0.6 The space group of the crystal is R3m, and the unit cell parameters are: α=β=90°, γ=120°, Z=3, Its crystal structure is Figure 1 shown.

[0073] The nonlinear optical crystal ZnBrSePZN obtained in Example 2 0.8 P 0.2 Se 0.2 Br 0.6 The X-ray powder diffraction of Figure 2 As shown in the figure, it can be seen that the Zn 0.8 P 0.2 Se 0.2 Br 0.6 The XRD pattern of the crystal is consistent with the theoretical simulation XRD pattern, which shows that Example 2 successfully obtained Zn 0.8 P 0.2 Se 0.2 Br 0.6 Pure phase of nonlinear optical crystals.

[0074] Example 3

[0075] Preparation of Zn by gas phase transport method 0.8 P 0.2 Se 0.2 Br 0.6 Infrared nonlinear optical crystals.

[0076] The chemical reaction equation is: 0.5Zn3P2+ZnSe+5ZnBr2=5Zn 0.8 P 0.2 Se 0.2 Br 0.6 +3.5ZnBr2, the specific steps are as follows:

[0077] The raw materials Zn3P2, ZnSe and ZnBr2 were uniformly mixed and ground in a molar ratio of 0.5:1:5 to make the molar ratio of Zn, P, Se and Br be 8.5:1:1:10, and then placed in a quartz tube and evacuated to 10 -3 Pa and melt seal it, put the sealed quartz tube into a horizontal double temperature zone tube furnace, put the material zone at the high temperature end, and heat the high temperature end (ie, evaporation end) to 600°C at a rate of 20°C / h; heat the low temperature end (ie, crystallization end) in the horizontal double temperature zone tube furnace to 550°C at a rate of 20°C / h, and calcine at a constant temperature for 100 hours. After calcination, cool down the high temperature end to 350°C at a rate of 2°C / h, and cool the low temperature end to 280°C at a rate of 2°C / h, and then cool it to room temperature at a rate of 5°C / h. Cut it open, and the excess white flaky ZnBr2 and the cyan Zn 0.8 P0.2 Se 0.2 Br 0.6 The crystals are separated mechanically.

[0078] The nonlinear optical crystal ZnBrSePZN obtained in this embodiment 0.8 P 0.2 Se 0.2 Br 0.6 The nonlinear optical crystal ZnBrSePZN obtained in Example 2 0.8 P 0.2 Se 0.2 Br 0.6 The structure is consistent.

[0079] The nonlinear optical crystal ZnBrSePZN obtained in this embodiment 0.8 P 0.2 Se 0.2 Br 0.6 The UV transmission spectrum of Figure 3 As shown in the figure, it can be seen that the nonlinear optical crystal Zn 0.8 P 0.2 Se 0.2 Br 0.6 The ultraviolet cutoff edge is located at 428nm, and the corresponding optical band gap is 2.90eV.

[0080] The test shows that the bromine-selenium-phosphorus-zinc nonlinear optical crystal Zn obtained in Example 3 0.8 P 0.2 Se 0.2 Br 0.6 The crystal structure, space group, and unit cell parameters of the nonlinear optical crystal Zn of bromine selenide phosphorus zinc of Example 2 are similar to those of the nonlinear optical crystal Zn of Example 2. 0.8 P 0.2 Se 0.2 Br 0.6 same.

[0081] Example 4

[0082] Preparation of Zn compounds by high temperature solid phase method 0.8 P 0.2 Se 0.2 I 0.6 .

[0083] The chemical reaction equation is: 2.5Zn+P+Se+1.5ZnI2=5Zn 0.8 P 0.2 Se 0.2 I 0.6 , the specific steps are as follows:

[0084] The raw materials Zn, P, Se, and ZnI2 were uniformly mixed and ground in a molar ratio of 2.5:1:1:1.5 to make the molar ratio of element Zn, element P, element Se, and element I 4:1:1:3, and then placed in a quartz tube and evacuated to 10 -3 Pa and melt-seal, place the sealed quartz tube in a program-controlled muffle furnace; heat to 600°C at a rate of 10°C / h, keep constant temperature for 96 hours, reduce to 350°C at a rate of 3°C / h, and then reduce to room temperature at a rate of 5°C / h, close the muffle furnace, and after cooling to room temperature, take out the quartz tube and cut it open to obtain a green-yellow block of Zn 0.8 P 0.2 Se 0.2 I 0.6 The compound has an X-ray powder diffraction pattern of Figure 2 As shown in the figure, it can be seen that the Zn 0.8 P 0.2 Se 0.2 I 0.6 The XRD pattern of the compound is consistent with the theoretical simulation XRD pattern, which shows that Example 4 successfully synthesized the compound Zn 0.8 P 0.2 Se 0.2 Br 0.6 of pure phase.

[0085] Example 5

[0086] Preparation of Zn by self-solvent method 0.8 P 0.2 Se 0.2 I 0.6 Infrared nonlinear optical crystals.

[0087] The chemical reaction equation is: 0.5Zn3P2+ZnSe+6ZnI2=5Zn 0.8 P 0.2 Se 0.2 I 0.6 +4.5ZnI2, the specific steps are as follows:

[0088] The raw materials Zn3P2, ZnSe and ZnI2 were uniformly mixed and ground in a molar ratio of 0.5:1:6 to make the molar ratio of element Zn, element P, element Se and element I 8.5:1:1:12, and then placed in a quartz tube and evacuated to 10 -3 Pa and melt seal, put the sealed quartz tube into a program-controlled muffle furnace; heat it to 650℃ at a rate of 10℃ / h, keep it constant for 96 hours, then reduce it to 350℃ at a rate of 3℃ / h, and then reduce it to room temperature at a rate of 5℃ / h, close the muffle furnace, and after cooling to room temperature, take out the quartz tube and cut it open. 0.8 P0.2 Se 0.2 I 0.6 The crystals are separated mechanically.

[0089] The test shows that the Zn prepared in this embodiment 0.8 P 0.2 Se 0.2 I 0.6 The space group of the crystal is R3m, and the unit cell parameters are: α=β=90°, γ=120°, Z=3,

[0090] The iodine-selenium-phosphorus-zinc nonlinear optical crystal Zn obtained in this embodiment 0.8 P 0.2 Se 0.2 I 0.6 The X-ray powder diffraction of Figure 2 As shown in the figure, it can be seen that the iodine-selenium-phosphorus-zinc nonlinear optical crystal Zn obtained in this embodiment 0.8 P 0.2 Se 0.2 I 0.6 The XRD pattern of the ZnO2O3 was consistent with the theoretical simulation XRD pattern, which showed that Example 5 successfully obtained ZnO2O3. 0.8 P 0.2 Se 0.2 Br 0.6 Pure phase of nonlinear optical crystals.

[0091] Example 6

[0092] Preparation of Zn by gas phase transport method 0.8 P 0.2 Se 0.2 I 0.6 Infrared nonlinear optical crystals.

[0093] The chemical reaction equation is: 0.5Zn3P2+ZnSe+5ZnI2=5Zn 0.8 P 0.2 Se 0.2 I 0.6 +3.5ZnI2, the specific steps are as follows:

[0094] The raw materials Zn3P2, ZnSe and ZnI2 were uniformly mixed and ground in a molar ratio of 0.5:1:5 to make the molar ratio of element Zn, element P, element Se and element I be 8.5:1:1:10, and then placed in a quartz tube and evacuated to 10 -3Pa and melt seal, put the sealed quartz tube into a horizontal double temperature zone tube furnace, heat the high temperature end (ie evaporation end) to 650℃ at a rate of 20℃ / h, heat the low temperature end (ie crystallization end) in the horizontal double temperature zone tube furnace to 580℃ at a rate of 20℃ / h, and calcine at a constant temperature for 100 hours. After calcination, cool down the high temperature end or evaporation end to 350℃ at a rate of 2℃ / h, cool the low temperature end to 280℃ at a rate of 2℃ / h, and then cool to room temperature at a rate of 5℃ / h. Cut it open, and the excess white flaky ZnI2 and the green-yellow Zn 0.8 P 0.2 Se 0.2 I 0.6 The crystals are separated mechanically.

[0095] The nonlinear optical crystal ZnBrSePZN obtained in this embodiment 0.8 P 0.2 Se 0.2 I 0.6 The nonlinear optical crystal ZnBrSePZN obtained in Example 5 0.8 P 0.2 Se 0.2 I 0.6 consistent.

[0096] The nonlinear optical crystal ZnBrSePZN obtained in this embodiment 0.8 P 0.2 Se 0.2 I .6 The UV transmittance of Figure 3 As shown in the figure, it can be seen that its ultraviolet cutoff edge is located at 443nm, and the corresponding optical band gap is 2.80eV.

[0097] The test shows that the iodine-selenium-phosphorus-zinc nonlinear optical crystal Zn obtained in Examples 5-6 0.8 P 0.2 Se 0.2 I 0.6 The crystal structure, space group, and unit cell parameters of the iodine-selenium-phosphorus-zinc nonlinear optical crystal Zn of Example 4 are similar to those of the iodine-selenium-phosphorus-zinc nonlinear optical crystal Zn 0.8 P 0.2 Se 0.2 I 0.6 Basically the same.

[0098] Example 7

[0099] Take the nonlinear optical crystal Zn obtained in Example 3 0.8 P 0.2 Se 0.2 Br 0.6 and the nonlinear optical crystal Zn obtained in Example 6 0.8 P 0.2 Se 0.2 I0.6 The Zn content was determined using a Shimadzu SolidSpec-3700DUV spectrophotometer. 0.8 P 0.2 Se 0.2 Br 0.6 、Zn 0.8 P 0.2 Se 0.2 I 0.6 The UV-visible-near infrared transmission spectrum in the wavelength range of 190 to 2500 nm. The transmission spectrum was measured using a 0.5 mm thick wafer as the substrate. The results are as follows Figure 3 As shown. Figure 3 It can be seen that Zn 0.8 P 0.2 Se 0.2 Br 0.6 、Zn 0.8 P 0.2 Se 0.2 I 0.6 The band gap values are 2.90eV and 2.80eV respectively.

[0100] The nonlinear optical crystal ZnBrSePZN obtained in Example 2 0.8 P 0.2 Se 0.2 Br 0.6 It also has the same properties as the nonlinear optical crystal Zn of bromine selenium phosphorus zinc in Example 3. 0.8 P 0.2 Se 0.2 Br 0.6 The same band gap value. The iodine-selenium-phosphorus-zinc nonlinear optical crystal Zn obtained in Example 5 0.8 P 0.2 Se 0.2 I 0.6 It also has the same properties as the iodine-selenium-phosphorus-zinc nonlinear optical crystal Zn in Example 4. 0.8 P 0.2 Se 0.2 I 0.6 Same band gap value.

[0101] Example 8

[0102] Take the nonlinear optical crystal Zn obtained in Example 2 0.8 P 0.2 Se 0.2 Br 0.6 and the nonlinear optical crystal Zn obtained in Example 5 0.8 P 0.2 Se 0.2 I 0.6Commercial AgGaS2 crystals were sieved through a mesh sieve into 6 types of particles, namely 25-45μm, 45-58μm, 58-75μm, 75-106μm, 106-150μm and 150-212μm, and placed in a container with a thickness of two layers of filter paper (about 1mm) and a diameter of 8mm to test the frequency doubling effect. Silver gallium sulfide was used as a reference sample. The fundamental frequency light was a 2050nm laser pulse (10ns, 3mJ, 10Hz) emitted by a Q-switched Nd:YAG laser. The back end of the frequency doubling light detector was connected to a DS1052E 50-MHz oscilloscope to convert the light signal into a voltage value. Therefore, by comparing the voltage values of the sample and the reference sample, the experimental frequency doubling coefficient can be obtained. The frequency doubling intensity and sample particle size curve under the 2050nm laser test is shown in Figure 4 .from Figure 4 It can be seen that Zn 0.8 P 0.2 Se 0.2 Br 0.6 and Zn 0.8 P 0.2 Se 0.2 I 0.6 The frequency-doubled intensity output by the crystal is 4.2 and 5.0 times that of the standard sample AgGaS2 under the same conditions.

[0103] The iodine-selenium-phosphorus-zinc nonlinear optical crystal Zn obtained in Example 3 0.8 P 0.2 Se 0.2 Br 0.6 It also has the same properties as the iodine-selenium-phosphorus-zinc nonlinear optical crystal Zn in Example 2. 0.8 P 0.2 Se 0.2 Br 0.6 The iodine-selenium-phosphorus-zinc nonlinear optical crystal Zn obtained in Example 6 0.8 P 0.2 Se 0.2 I 0.6 It also has the same properties as the iodine-selenium-phosphorus-zinc nonlinear optical crystal Zn in Example 5. 0.8 P 0.2 Se 0.2 I 0.6 Basically the same doublet intensity.

[0104] The above describes the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the scope of protection of the present invention.

Claims

1. A selenium phosphorus zinc halide compound, characterized in that Its chemical formula is Zn 0.8 P 0.2 Se 0.2 X 0.6 , X is selected from F, Cl, Br or I.

2. The method for preparing the selenium phosphorus zinc halide compound according to claim 1, wherein The preparation method comprises: mixing a Zn source, a P source, a Se source and an X source, and calcining at a high temperature to obtain the selenium halogenide phosphorus zinc compound.

3. The preparation method according to claim 2, wherein The molar ratio of the element Zn in the Zn source, the element P in the P source, the element Se in the Se source, and the element X in the X source is 1-8.5:1:1:3-12, preferably 1-5:1:1:3-4 or 7.5-8.5:1:1:8-12; Preferably, the Zn source is selected from at least one of Zn element, Zn3P2, ZnSe, ZnBr2 and ZnI2; Preferably, the P source is selected from at least one of P element and Zn3P2; Preferably, the Se source is selected from at least one of Se element and ZnSe; Preferably, the X source is selected from ZnBr2 and ZnI2; Preferably, the high-temperature calcination temperature is 550°C-650°C, exemplified by 550°C, 560°C, 570°C, 580°C, 590°C, 600°C or 650°C; the calcination time is 48 hours-120 hours; and the heating rate is 10°C / h-30°C / h.

4. The preparation method according to claim 2 or 3, wherein The high-temperature calcination is carried out in a horizontal dual-temperature zone tubular furnace; Preferably, during the high-temperature calcination, the high-temperature end of the horizontal dual-temperature zone tubular furnace is heated to 600-650° C. at a rate of 10° C. / h-25° C. / h, and the low-temperature end of the horizontal dual-temperature zone tubular furnace is heated to 550-580° C. at a rate of 15° C. / h-25° C. / h, and the constant-temperature calcination is performed for 48 hours to 120 hours; Preferably, after calcination, the high temperature end is lowered to 300-350°C at a rate of 1-3°C / h, the low temperature end is lowered to 250-280°C at a rate of 1-3°C / h, and then cooled to room temperature at a rate of 4-6°C / h.

5. A selenium phosphorus zinc halide crystal, characterized in that: Its chemical formula is Zn 0.8 P 0.2 Se 0.2 X 0.6 , X is selected from F, Cl, Br or I.

6. The method for preparing the selenium phosphorus zinc halide crystal according to claim 5, wherein: The preparation method comprises: mixing a Zn source, a P source, a Se source and an X source, and calcining the mixture at a high temperature to obtain the selenium halogenide phosphorus zinc crystal.

7. The preparation method according to claim 6, wherein The molar ratio of the element Zn in the Zn source, the element P in the P source, the element Se in the Se source, and the element X in the X source is 1-8.5:1:1:3-12, preferably 1-5:1:1:3-4 or 7.5-8.5:1:1:8-12; Preferably, the Zn source is selected from at least one of Zn element, Zn3P2, ZnSe, ZnBr2 and ZnI2; Preferably, the P source is selected from at least one of P element and Zn3P2; Preferably, the Se source is selected from at least one of Se element and ZnSe; Preferably, the X source is selected from at least one of ZnBr2 and ZnI2; Preferably, the high-temperature calcination temperature is 550° C.-650° C.; the calcination time is 48 hours-120 hours; and the heating rate is 10° C. / h-30° C. / h.

8. The preparation method according to claim 6 or 7, characterized in that The high-temperature calcination is carried out in a horizontal dual-temperature zone tubular furnace; Preferably, during the high-temperature calcination, the high-temperature end of the horizontal dual-temperature zone tubular furnace is heated to 600-650° C. at a rate of 10° C. / h-25° C. / h, and the low-temperature end of the horizontal dual-temperature zone tubular furnace is heated to 550-580° C. at a rate of 15° C. / h-25° C. / h, and the constant-temperature calcination is performed for 48 hours to 120 hours; Preferably, after calcination, the high temperature end is lowered to 300-350°C at a rate of 1-3°C / h, the low temperature end is lowered to 250-280°C at a rate of 1-3°C / h, and then cooled to room temperature at a rate of 4-6°C / h.

9. The selenium phosphorus zinc halide compound according to claim 1 and / or the selenium phosphorus zinc halide crystal according to claim 5 are used in the field of nonlinear optics or in the mid-infrared band.

10. A nonlinear optical device, characterized in that: The nonlinear optical device comprises the selenium halogenide phosphorus zinc compound according to claim 1 and / or the selenium halogenide phosphorus zinc crystal according to claim 5.

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