An inorganic compound crystal, its preparation method and application

Abstract

This application discloses an inorganic compound crystal, its preparation method, and its applications. The inorganic compound crystal has the chemical formula Ga2(OH)(TeO3)(Te2O5)Br, belongs to the orthorhombic crystal system, has a space group of Pca21, and unit cell parameters α=β=γ=90°, Z=4. The inorganic compound crystal is prepared using a hydrothermal method. Under 1064nm laser irradiation, the powder frequency doubling intensity of the inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br is 9.8 times that of KH2PO4(KDP), and phase matching can be achieved, indicating its significant potential application value as a nonlinear optical material.

Description

Technical Field

[0001] This application relates to an inorganic compound crystal, its preparation method, and its application, belonging to the field of inorganic materials. Background Technology

[0002] Nonlinear optical crystals are a class of functional materials widely used in optoelectronic technology. Their unique nonlinear optical effects make them crucial in various fields such as laser processing, optical communication, and information storage. Under the influence of strong lasers, these crystals can generate nonlinear effects such as frequency doubling, sum-frequency generation, and difference-frequency generation, thereby achieving laser frequency conversion. Through these frequency conversion processes, nonlinear optical crystals can convert infrared or visible light into light in other wavelength bands, significantly broadening the application range of lasers.

[0003] Currently, practically used nonlinear optical crystal materials include LiB3O5 (LBO), β-BaB2O4 (BBO), KH2PO4 (KDP), KTiOPO4 (KTP), α-AgIO3, AgGaS2 (AGS), and ZnGeP2. These materials are widely used in laser devices, fiber optic communication, and quantum optics due to their strong nonlinear coefficients, stable physical properties, and excellent optical characteristics. With the development of science and technology, the application prospects of nonlinear optical crystals in emerging fields such as optoelectronic devices and quantum communication are becoming increasingly broad. Therefore, developing new nonlinear optical crystals with superior performance is of great significance. Summary of the Invention

[0004] According to the first aspect of this application, an inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br is provided. This inorganic compound crystal exhibits a strong second harmonic generation effect, with its powder frequency doubling intensity being 9.8 times that of KH2PO4(KDP) under 1064nm laser irradiation, and it can achieve phase matching, making it a nonlinear optical material with potential application value.

[0005] An inorganic compound crystal, wherein the chemical formula of the inorganic compound crystal is Ga2(OH)(TeO3)(Te2O5)Br.

[0006] Optionally, in the crystal structure of the inorganic compound crystal, Ga(1)O6 and Ga(2)O6 octahedra are connected by sharing edges to form Ga2O. 10 Dimers, which are interconnected by oxygen atoms to form one-dimensional gallium oxide wavy chains along the c-axis;

[0007] Gallium oxide wavy chains are bridged by Te(1)O3 trigonal pyramids to form a two-dimensional gallium telluride layer parallel to the bc plane;

[0008] The two-dimensional gallium telluride layer is further connected by Te2O5 dimers to form a three-dimensional cation framework with Ga3Te3 hexa-polyhedral annular channels along the b-axis.

[0009] The isolated bromide anion is located in the six-membered polyhedral annular channel to balance the charge.

[0010] The crystal structure of the inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br is as follows: Figure 1 As shown. In this structure, Ga(1)O6 and Ga(2)O6 octahedra are connected by sharing edges to form Ga2O. 10 Dimers are interconnected by oxygen atoms to form one-dimensional gallium oxide wavy chains along the c-axis; the one-dimensional gallium oxide chains are bridged by Te(1)O3 trigonal pyramids to form a two-dimensional gallium telluride layer parallel to the bc plane; the two-dimensional gallium telluride layer is further connected by Te2O5 dimers to form a three-dimensional cation framework with Ga3Te3 hexa-membered polyhedral annular channels along the b-axis. Isolated bromide anions are located in the hexa-membered polyhedral annular channels, forming a Ga2(OH)(TeO3)(Te2O5)Br structure.

[0011] Optionally, the inorganic compound crystal belongs to the orthorhombic crystal system with space group Pca21;

[0012] Optionally, the unit cell parameters of the inorganic compound crystal are: α=β=γ=90.000°, Z=4;

[0013] Preferably, the cell parameters are:

[0014] Preferably, the cell parameters are:

[0015] Specifically, the unit cell parameters are α=β=γ=90°, Z=4.

[0016] Optionally, the powder frequency doubling intensity of the inorganic compound crystal under 1064nm laser irradiation is 8 to 12 times that of KH2PO4 (KDP).

[0017] Optionally, the powder frequency doubling intensity of the inorganic compound crystal under 1064nm laser irradiation is 9 to 11 times that of KH2PO4 (KDP).

[0018] Optionally, the powder frequency doubling intensity of the inorganic compound crystal under 1064nm laser irradiation is 9.8 times that of KH2PO4 (KDP).

[0019] Optionally, the ultraviolet absorption cutoff wavelength of the inorganic compound crystal is 270–310 nm.

[0020] Optionally, the ultraviolet absorption cutoff wavelength of the inorganic compound crystal is 280–310 nm.

[0021] Optionally, the ultraviolet absorption cutoff wavelength of the inorganic compound crystal is 289 nm.

[0022] Optionally, the inorganic compound crystals lose no more than 5% of their weight at 420°C.

[0023] Optionally, the inorganic compound crystals lose no more than 3% of their weight at 420°C, and the phase does not change.

[0024] That is, the inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br can be stabilized up to 420℃.

[0025] According to a second aspect of this application, a method for preparing the aforementioned inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br is provided. This preparation method employs hydrothermal crystallization, is simple in process, and can yield high-purity, highly crystallized inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br material.

[0026] A mixture of raw materials containing gallium, tellurium, bromine, and water is placed in a sealed container and crystallized to obtain the inorganic compound crystal.

[0027] Optionally, the molar ratio of gallium, tellurium, bromine, and water in the raw material mixture is:

[0028] Ga: Te: Br: H2O=1~4: 0.5~4.5: 0.1~2.0: 10~300.

[0029] Optionally, the molar ratio of gallium, tellurium, bromine, bismuth, and water in the raw material mixture is:

[0030] Ga: Te: Br: H2O=1.3~3.5: 0.8~4.0: 0.5~1.8: 30~200.

[0031] Optionally, the molar ratio of gallium, tellurium, bromine, bismuth, and water in the raw material mixture is:

[0032] Ga: Te: Br: H2O=1.5~3.2: 1.0~3.5: 0.8~1.5: 50~100.

[0033] Optionally, the raw material mixture also includes bismuth.

[0034] The molar ratio of gallium and bismuth is Ga:Bi = 1-4:0.1-3.

[0035] Optionally, the molar ratio of gallium and bismuth is: Ga:Bi = 1.3~3.5:0.2~2.

[0036] Preferably, the molar ratio of gallium and bismuth is Ga:Bi = 1.5-3.2:0.3-1.

[0037] Optionally, in the raw material mixture, gallium is derived from at least one of gallium oxide, gallium chloride, gallium nitrate, and gallium bromide; tellurium is derived from at least one of tellurium dioxide, sodium tellurite, potassium tellurite, and telluric acid; and bromine is derived from at least one of sodium bromide, bismuth bromide, potassium bromide, hydrobromic acid, cesium bromide, calcium bromide, cuprous bromide, lead bromide, lithium bromide, stannous bromide, and silver bromide.

[0038] Optionally, the bismuth element is derived from at least one of bismuth bromide, bismuth chloride, bismuth oxide, and bismuth nitrate. The bismuth element is used as an auxiliary agent.

[0039] Preferably, in the raw material mixture, gallium is derived from gallium trioxide; tellurium from tellurium dioxide; bromine from hydrobromic acid; and bismuth from bismuth bromide.

[0040] Optionally, the hydrobromic acid is an aqueous solution of hydrogen bromide with a concentration of 40 wt% to 100 wt%.

[0041] Optionally, the crystallization temperature is 150℃~300℃, and the crystallization time is 24 hours~200 hours.

[0042] Preferably, the crystallization temperature is 180℃~280℃, and the crystallization time is 50 hours~170 hours.

[0043] Preferably, the crystallization temperature is 190℃~270℃, and the crystallization time is 72 hours~150 hours.

[0044] Optionally, the upper limit of the crystallization temperature is selected from 300℃, 290℃, 280℃, 270℃, 260℃, 250℃, 240℃, 230℃, 220℃, 210℃, 200℃, 190℃, 180℃, 170℃, or 160℃; the lower limit is selected from 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, or 290℃.

[0045] Optionally, the upper limit of the crystallization time is selected from 200h, 190h, 180h, 170h, 150h, 120h, 110h, 100h, 96h, 80h, 72h, 70h, 60h, 50h, 48h, 36h, or 30h; the lower limit is selected from 24h, 30h, 36h, 48h, 50h, 60h, 70h, 72h, 80h, 96h, 100h, 110h, 120h, 150h, 170h, 180h, or 190h.

[0046] Optionally, after crystallization, the mixture is cooled to room temperature, separated, and dried to obtain the inorganic compound crystals.

[0047] Optionally, the cooling rate is 0.5–15 °C / h.

[0048] Preferably, the cooling rate is 2–12 °C / h.

[0049] Optionally, the upper limit of the cooling rate is selected from 15℃ / h, 13℃ / h, 12℃ / h, 10℃ / h, 8℃ / h, 6℃ / h, 4℃ / h, 3℃ / h, 2℃ / h or 1℃ / h; the lower limit is selected from 0.5℃ / h, 1℃ / h, 2℃ / h, 3℃ / h, 4℃ / h, 6℃ / h, 8℃ / h, 10℃ / h, 12℃ / h or 13℃ / h.

[0050] In a preferred embodiment, the method for preparing the inorganic compound crystal includes the following steps:

[0051] (a) Place a mixture of raw materials containing gallium, tellurium, bromine, bismuth and water in a reaction vessel with a polytetrafluoroethylene liner, seal it and crystallize it at a crystallization temperature of 180 to 300°C for more than 24 hours.

[0052] (b) After crystallization, the system is cooled to room temperature at a rate not exceeding 15°C / h. The solid sample obtained after separation and drying is the inorganic compound crystal.

[0053] The inorganic compound crystals prepared by the hydrothermal method are colorless and transparent rod-shaped crystals.

[0054] According to a third aspect of this application, an application of the aforementioned inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br as a nonlinear optical crystal material is provided.

[0055] According to a fourth aspect of this application, an application of the inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br described above in optical devices is provided.

[0056] In this application, "room temperature" refers to 25°C.

[0057] The beneficial effects that this application can produce include:

[0058] 1) The inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br provided in this application exhibits a strong second harmonic generation effect. Under 1064nm laser irradiation, its powder frequency doubling intensity is 9.8 times that of KH2PO4(KDP), and it can achieve phase matching, making it a nonlinear optical material with potential application value.

[0059] 2) The inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br provided in this application has a high transmittance in the spectral range of 289 to 1500 nm, and its ultraviolet absorption cutoff wavelength is about 289 nm.

[0060] 3) The inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br provided in this application can be stabilized up to 420℃ and has excellent thermal stability.

[0061] 4) The method for preparing the inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br provided in this application employs a hydrothermal crystallization method to grow colorless rod-shaped Ga2(OH)(TeO3)(Te2O5)Br crystals. The method is simple and can yield high-purity, highly crystallizable inorganic compound Ga2(OH)(TeO3)(Te2O5)Br crystal materials. Attached Figure Description

[0062] Figure 1 This is a schematic diagram of the crystal structure of the inorganic compound Ga2(OH)(TeO3)(Te2O5)Br, where... Figure 1 (a) is a one-dimensional gallium oxide chain; Figure 1 (b) is a two-dimensional gallium telluride layer; Figure 1 (c) shows the crystal structure of the compound.

[0063] Figure 2 It is sample 1 # A comparison was made between the X-ray diffraction pattern obtained by fitting the crystal structure determined by single-crystal X-ray diffraction and the X-ray diffraction pattern obtained by grinding the sample into powder.

[0064] Figure 3 It is sample 1 # The harmonic intensity and phase matching diagram.

[0065] Figure 4 It is sample 1 # The ultraviolet-visible-near-infrared diffuse reflectance spectrum.

[0066] Figure 5 It is sample 1 # Thermogravimetric diagram. Detailed Implementation

[0067] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments. Unless otherwise specified, the raw materials and reagents used in this application are all commercially purchased and used directly without processing, and the instruments and equipment used adopt the schemes and parameters recommended by the manufacturers.

[0068] Hydrothermal synthesis of the sample in Example 1

[0069] The raw materials were prepared according to a specific molar ratio and placed in a polytetrafluoroethylene-lined reactor. The mixture was then heated to the crystallization temperature and held at that temperature for a period of time. The system temperature was then lowered to room temperature at a controlled cooling rate. After filtration and washing, a colorless, rod-shaped crystal sample was obtained, which is the sample of the inorganic compound crystal.

[0070] The sample number, raw material type and amount, crystallization temperature and holding time, and cooling rate are shown in Table 1. Among them, HBr comes from a 40wt% HBr aqueous solution, and the molar ratio refers to the molar ratio of gallium, tellurium, bromine, bismuth, and water in the raw material mixture.

[0071] Table 1

[0072]

[0073]

[0074] Example 2 Crystal Structure Analysis

[0075] Single-crystal X-ray diffraction and powder X-ray diffraction methods were used to analyze sample 1. # ~4 # Perform structural analysis.

[0076] Single-crystal X-ray diffraction was performed using an Agilent Technologies SuperNova CCD single-crystal X-ray diffractometer. Data was collected at 298 K, using graphite-monochromatic Mo-Kα rays with a scanning mode of ω-2θ. Data were processed using the Multi-Scan method for absorption correction. Structural analysis was performed using the Olex2 1.5 package; the positions of heavy atoms were determined using a direct method, and the coordinates of the remaining atoms were obtained using the difference Fourier synthesis method. The results were then analyzed using an F-based method. 2 The full matrix least squares method is used to refine the coordinates and anisotropic thermal parameters of all atoms.

[0077] Powder X-ray diffraction was performed on a Miniflex 600 X-ray powder diffractometer from Rigaku Corporation, Japan. The test conditions were a fixed target, a monochromatic Cu-Kα light source, and a wavelength of [missing information]. The voltage and current are 30kV / 15A, the scanning range is 10~70°, and the scanning step is 0.02°.

[0078] Among them, the single-crystal X-ray diffraction results showed that sample 1 # ~4 # All have the chemical formula Ga2(OH)(TeO3)(Te2O5)Br, belong to the orthorhombic crystal system, space group Pca21, and cell parameters [missing information]. α=β=γ=90.000°, Z=4. The crystal structure of the inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br is as follows: Figure 1 As shown in the diagram. In this structure, Ga(1)O6 and Ga(2)O6 octahedra are connected by sharing edges to form Ga2O. 10 Dimers, these dimers are interconnected by oxygen atoms to form one-dimensional wavy gallium oxide chains along the c-axis; the gallium oxide chains are bridged by Te(1)O3 trigonal pyramids to form a two-dimensional gallium telluride layer parallel to the bc plane; the two-dimensional gallium telluride layer is further connected by Te2O5 dimers to form a three-dimensional cation framework with Ga3Te3 hexa-membered polyhedral channels along the b-axis; isolated bromide anions are located in the hexa-membered polyhedral channels, forming the structure Ga2(OH)(TeO3)(Te2O5)Br. Figure 1 ).

[0079] With sample 1 # It is a typical example, belonging to the orthorhombic crystal system, with space group Pca21 and cell parameters of . α=β=γ=90°, Z=4.

[0080] Powder X-ray diffraction results show that sample 1 # ~4 # On the XRD spectrum, the peak positions are basically the same, but the peak intensities of each sample are slightly different.

[0081] With sample 1 # As a typical example, such as Figure 2 As shown, based on the crystal structure resolved by single-crystal X-ray diffraction, the fitted X-ray diffraction pattern is consistent with that of sample 1. # The X-ray diffraction patterns obtained after grinding the samples into powder showed consistent peak positions and intensities, indicating that the obtained samples all had high purity.

[0082] Example 3: Frequency doubling test experiment and results

[0083] With sample 1 #For example, frequency doubling tests were performed on the inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br.

[0084] The specific steps are as follows: A 1064nm laser is used as the fundamental frequency light to irradiate the crystal powder under test. The generated second harmonic is detected using a photomultiplier tube, and the harmonic intensity is displayed on an oscilloscope. The crystal sample to be tested is sieved using a standard sieve to obtain crystals of different particle sizes: 45-53μm, 53-75μm, 75-105μm, 105-150μm, 150-210μm, and 210-300μm. The trend of the harmonic frequency doubling signal with particle size is observed to determine whether phase matching can be achieved. Under the same test conditions, the intensity of the second harmonic generated by the sample under test is compared with the intensity of the second harmonic generated by the reference crystal KH2PO4 (KDP) to obtain the relative magnitude of the harmonic frequency doubling effect of the sample.

[0085] Test results are as follows Figure 3 As shown, the second harmonic generation intensity of the inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br measured at 1064 nm is 9.8 times that of KH2PO4(KDP), and phase matching can be achieved.

[0086] Example 4: Diffuse Reflectance Absorption Spectroscopy Test

[0087] With sample 1 # Diffuse reflectance absorption spectroscopy of the inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br was performed using a PerkinElmer Lambda-950 UV-Vis-NIR spectrophotometer. The crystal sample was ground into powder, and BaSO4 was used as the reference substrate. The test results are as follows: Figure 4 As shown, the crystal of compound Ga2(OH)(TeO3)(Te2O5)Br has a wide transmission range, with high transmittance in the spectral range of 289–1500 nm and an ultraviolet absorption cutoff wavelength of approximately 289 nm.

[0088] Thermogravimetric Analysis of Sample in Example 5

[0089] With sample 1 # For example, thermogravimetric analysis was performed on the inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br using a NETZSCH STA449F3 thermogravimetric analyzer. The results are as follows: Figure 5 As shown in the figure, Ga2(OH)(TeO3)(Te2O5)Br crystals can be stabilized up to 420℃.

[0090] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. An inorganic compound crystal, characterized in that, The chemical formula of the inorganic compound crystal is Ga2(OH)(TeO3)(Te2O5)Br; The inorganic compound crystal belongs to the orthorhombic crystal system, with space group [space group number missing]. Pca twenty one; The unit cell parameters of the inorganic compound crystal are as follows: a = 16.0138(4) Å, b = 7.0036(2) Å, c = 8.4023(2) Å, α = β = γ = 90°, Z = 4.

2. The inorganic compound crystal according to claim 1, characterized in that, In the crystal structure of the inorganic compound crystal, Ga(1)O6 and Ga(2)O6 octahedra are connected by sharing edges to form Ga2O. 10 Dimers, which are interconnected by oxygen atoms, form one-dimensional wavy gallium oxide chains along the c-axis; Gallium oxide chains are bridged by Te(1)O3 trigonal pyramids to form a two-dimensional gallium telluride layer parallel to the bc plane; The two-dimensional gallium telluride layer is further connected by Te2O5 dimers to form a three-dimensional cation framework with Ga3Te3 hexa-polyhedral ring channels along the b-axis; Isolated bromide anions reside in the six-membered polyhedral channels to balance their charges.

3. The inorganic compound crystal according to claim 1, characterized in that, The intensity of the powder frequency harmonics of the inorganic compound crystal measured under a 1064 nm laser is 8 to 12 times that of KH2PO4.

4. The inorganic compound crystal according to claim 1, characterized in that, The ultraviolet absorption cutoff wavelength of the inorganic compound crystal is 270~310 nm.

5. The inorganic compound crystal according to claim 1, characterized in that, The inorganic compound crystals lose no more than 5% of their weight at 420 °C.

6. The method for preparing inorganic compound crystals according to any one of claims 1 to 5, characterized in that, A mixture of raw materials containing gallium, tellurium, bromine, and water is placed in a sealed container and crystallized to obtain the inorganic compound crystal.

7. The preparation method according to claim 6, characterized in that, The molar ratio of gallium, tellurium, bromine, and water in the raw material mixture is as follows: Ga: Te: Br: H2O = 1~4: 0.5~4.5: 0.1~2.0: 10~300.

8. The preparation method according to claim 6, characterized in that, The molar ratio of gallium, tellurium, bromine, and water in the raw material mixture is as follows: Ga: Te: Br: H2O = 1.3~3.5: 0.8~4.0: 0.5~1.8: 30~200.

9. The preparation method according to claim 6, characterized in that, The molar ratio of gallium, tellurium, bromine, and water in the raw material mixture is as follows: Ga: Te: Br: H2O = 1.5~3.2: 1.0~3.5: 0.8~1.5: 50~100.

10. The preparation method according to claim 6, characterized in that, The raw material mixture also includes bismuth. The molar ratio of gallium and bismuth is Ga:Bi = 1~4: 0.1~3.

11. The preparation method according to claim 10, characterized in that, The molar ratio of gallium and bismuth is: Ga:Bi = 1.3~3.5: 0.2~2.

12. The preparation method according to claim 10, characterized in that, The molar ratio of gallium and bismuth is Ga:Bi = 1.5~3.2: 0.3~1.

13. The preparation method according to claim 6, characterized in that, In the raw material mixture, gallium is derived from at least one of gallium oxide, gallium chloride, gallium nitrate, and gallium bromide; tellurium is derived from at least one of tellurium dioxide, sodium tellurite, potassium tellurite, and telluric acid; and bromine is derived from at least one of sodium bromide, bismuth bromide, potassium bromide, hydrobromic acid, cesium bromide, lead bromide, and lithium bromide.

14. The preparation method according to claim 10, characterized in that, The element bismuth comes from at least one of bismuth bromide, bismuth chloride, bismuth oxide, and bismuth nitrate.

15. The preparation method according to claim 6, characterized in that, The crystallization temperature is 150℃~300℃, and the crystallization time is 24 hours to 200 hours.

16. The preparation method according to claim 6, characterized in that, The crystallization temperature is 180℃~280℃, and the crystallization time is 50 hours~170 hours.

17. The preparation method according to claim 6, characterized in that, The crystallization temperature is 190℃~270℃, and the crystallization time is 72 hours~150 hours.

18. The preparation method according to claim 6, characterized in that, After crystallization, the mixture is cooled to room temperature, separated, and dried to obtain the inorganic compound crystals.

19. The preparation method according to claim 18, characterized in that, The cooling rate is 0.5~15℃ / h.

20. The preparation method according to claim 18, characterized in that, The cooling rate is 2~12℃ / h.

21. The application of the inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br according to any one of claims 1 to 5 as a nonlinear optical crystal material.

22. The application of the inorganic compound crystal Ga2(OH)(TeO3)(Te2O5)Br according to any one of claims 1 to 5 in optical devices.

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