Congruent molten halogen vanadate compound, vanadium zinc rubidium bromide nonlinear optical crystal as well as preparation method and application of homogeneous molten halogen vanadate compound and vanadium zinc rubidium bromide nonlinear optical crystal

Abstract

The invention discloses a congruent molten halogen vanadate compound, a vanadium zinc rubidium bromide nonlinear optical crystal as well as a preparation method and application of the vanadium zinc rubidium bromide nonlinear optical crystal. The chemical formula of the vanadate compound is Rb3ZnV4O12Br, the vanadium zinc rubidium bromide nonlinear optical crystal Rb3ZnV4O12Br can be prepared through the vanadate compound, the obtained nonlinear optical crystal is of a non-centrosymmetric structure and belongs to an orthorhombic system, the space group is C mm < 2 >, unit cell parameters are # imgabs0 # imgabs1 #, alpha is equal to 90 degrees, beta is equal to 90 degrees, gamma is equal to 90 degrees, and Z is equal to 2. The nonlinear optical crystal provided by the invention has the characteristics of high damage threshold, large nonlinear optical effect, high electro-optic coefficient, wide transmission range, easiness in crystal growth and the like, and the frequency doubling effect of the nonlinear optical crystal is 0.7-1.4 times that of an AGS crystal. The invention also discloses application of the nonlinear optical crystal in preparation of laser nonlinear optical composite functional devices, electro-optical crystal devices, lasers and other devices.

Description

Technical Field

[0001] The present invention relates to the field of artificial crystal technology, and more specifically to a homogeneous molten halogen vanadate compound, a vanadium zinc rubidium bromide nonlinear optical crystal, and a preparation method and application thereof. Background Art

[0002] Light can be divided into ultraviolet, visible, near-infrared, mid-infrared, far-infrared, terahertz and other frequency bands according to wavelength. Lasers of different frequency bands have different needs in the fields of national defense, medical treatment, environmental monitoring and remote sensing. However, solid-state lasers using laser crystals can often only produce lasers of a single wavelength. For example, the common Nd:YAG laser can only produce infrared lasers with a laser wavelength of 1064nm. On this basis, the common method of obtaining lasers in other wavelength ranges is to use nonlinear optical effects to perform frequency conversion on laser light sources with fixed wavelengths. Therefore, nonlinear optical crystals, as an important means of laser frequency regulation, have important research value.

[0003] Nonlinear optical effects include frequency conversion effects such as frequency doubling, difference frequency, and sum frequency. Crystal materials with the above effects are collectively referred to as nonlinear optical crystal materials. When light passes through a nonlinear optical crystal, in addition to the incident pump light, frequency doubling light and difference frequency light often appear. Frequency doubling light is generated through the second harmonic effect, and its frequency is doubled relative to the pump light. Difference frequency light is generated through the difference frequency generation process, which produces two lights of different frequencies, called messenger light and difference frequency light (lowest frequency), and the sum of their frequencies is equal to the pump light.

[0004] Currently, the commonly used nonlinear optical crystal materials are mainly divided into oxides and non-oxides. Common oxides include phosphates KDP (i.e. KH2PO4) and KTP (i.e. KTiOPO4), borates including BBO (i.e. β-BaB2O4), LBO (i.e. LiB3O5) crystals and KBBF (i.e. KBe2BO3F2), etc. Non-oxides include sulfides, selenides and phosphides AGS (i.e. AgGaS2), AGSe (i.e. AgGaSe2) and ZGP (i.e. ZnGeP2), etc.

[0005] For excellent second-order nonlinear optical crystal materials, their space group must be non-centrosymmetric, and they should have an appropriate refractive index to achieve phase matching, and have a sufficiently large frequency doubling coefficient, laser damage threshold, and a sufficiently wide light transmission range. However, the currently known crystals all have certain disadvantages. For example, crystals such as AGS, AGSe, and ZGP often have low transmittance, difficult crystal growth, and low laser damage threshold, which are not satisfactory in practical applications. Therefore, the task of exploring new nonlinear optical crystals with high efficiency, easy growth, and stable performance is imminent. Uniform melt crystals are particularly suitable for growing high-melting-point and large-size high-quality single crystal materials due to their precise control of growth conditions and high crystal quality in crystal growth. Summary of the invention

[0006] The first object of the present invention is to provide a homogeneous molten halogen vanadate compound.

[0007] The second object of the present invention is to provide a method for preparing the above-mentioned isocratic molten halogen vanadate compound.

[0008] The third object of the present invention is to provide a vanadium zinc rubidium bromide nonlinear optical crystal. The vanadium zinc rubidium bromide nonlinear optical crystal provided by the present invention has the characteristics of high damage threshold, large nonlinear optical effect, high electro-optic coefficient, wide transmission range and easy crystal growth, and the frequency doubling effect is about 0.7-1.4 times that of AGS crystal, and is suitable for visible light and mid-infrared light regions.

[0009] The fourth object of the present invention is to provide a method for preparing the vanadium zinc rubidium bromide nonlinear optical crystal as described above.

[0010] The fifth object of the present invention is to provide an application of the vanadium zinc rubidium bromide nonlinear optical crystal as described above in the preparation of laser nonlinear optical composite functional devices, electro-optical crystal devices or lasers.

[0011] In order to achieve the above first object, the present invention adopts the following technical scheme:

[0012] The present invention provides a homogeneous molten halogen vanadate compound, wherein the chemical formula of the vanadate compound is Rb3ZnV4O 12 Br.

[0013] In order to achieve the above second purpose, the present invention adopts the following technical solutions:

[0014] The present invention provides a method for preparing the vanadate compound as described above, wherein the vanadate compound is prepared by a high-temperature solid phase synthesis method or a hydrothermal method;

[0015] The solid phase synthesis method comprises the following steps:

[0016] The Rb-containing compound, Zn-containing compound, V-containing compound and Br-containing compound are ground and mixed, and the temperature is raised to 320-370°C at a rate of 10-50°C / h, and sintered at a constant temperature for 24-72h to obtain Rb3ZnV4O 12 Br polycrystalline powder;

[0017] The hydrothermal method comprises the following steps:

[0018] The Rb-containing compound, Zn-containing compound, V-containing compound and Br-containing compound are ground and mixed, and then put into a hydrothermal reactor, and water is added. The temperature is raised to 180-200°C at a rate of 10-50°C / h, and the temperature is kept constant for 24-72h, and then the temperature is lowered to room temperature at a rate of 10-50°C / day to obtain Rb3ZnV4O 12 Br polycrystalline powder.

[0019] Further, the Rb-containing compound is selected from one or more of Rb oxides, Rb hydroxides, Rb carbonates, Rb halides, Rb nitrates and Rb oxalates;

[0020] The Zn-containing compound is selected from one or more of Zn oxides, Zn hydroxides, Zn carbonates, Zn halides, Zn nitrates and Zn oxalates;

[0021] The V-containing compound is selected from one or more of V oxides, V hydroxides, V halides, V nitrates, V oxalates and ammonium vanadates;

[0022] The Br-containing compound is selected from one or more of Br rubidium salt, Br zinc salt and Br vanadium salt.

[0023] Furthermore, the molar ratio of the elements Rb, Zn, V and Br in the Rb-containing compound, the Zn-containing compound, the V-containing compound and the Br-containing compound is 3:1:4:1.

[0024] Furthermore, the amount of water used is 50-80% of the total volume of the hydrothermal reactor.

[0025] In order to achieve the third object, the present invention adopts the following technical solutions:

[0026] The present invention provides a vanadium zinc rubidium bromide nonlinear optical crystal, wherein the chemical formula of the vanadium zinc rubidium bromide nonlinear optical crystal is Rb3ZnV4O 12 Br, a non-centrosymmetric structure, belongs to the orthorhombic crystal system, the space group is Cmm2, and the unit cell parameters are α=90°, β=90°, γ=90°, Z=2,

[0027] In order to achieve the fourth objective, the present invention adopts the following technical solutions:

[0028] The present invention provides a method for preparing the vanadate nonlinear optical crystal as described above, comprising the following steps:

[0029] Putting the crystal growth material into a crystal growth furnace, heating it to 370-450° C. to obtain a melt, stirring it at a constant temperature for 24-72 hours, cooling it to 1-10° C. above the melt saturation point temperature and introducing a seed crystal, cooling it at a rate of 0.1-5° C. / day, and rotating the seed crystal rod at a rate of 10-50 r / min at the same time to start crystal growth, after the crystal growth is completed, lifting the crystal from the liquid surface, and then annealing it to room temperature at a cooling rate of no more than 100° C. / h to obtain the vanadium zinc rubidium bromide nonlinear optical crystal;

[0030] Wherein, the crystal growth cycle is 25-40 days.

[0031] The nonlinear optical crystal grown by the preparation method has the characteristics of high transparency, large crystal size, good optical quality, etc., and is particularly suitable for the processing of nonlinear optical devices and electro-optical devices.

[0032] Furthermore, the crystal growth material is selected from Rb3ZnV4O 12 Br polycrystalline powder or Rb3ZnV4O 12 A mixture of Br polycrystalline powder and flux. When the crystal growth material does not contain flux, it can be understood that the nonlinear optical crystal is prepared by the melt method, and when the crystal growth material contains flux, it can be understood that the nonlinear optical crystal is prepared by the flux method.

[0033] Furthermore, the Rb3ZnV4O 12 The molar ratio of Br polycrystalline powder to flux is 1:1-3; for example, the Rb3ZnV4O 12 The molar ratio of Br polycrystalline powder to flux can be 1:1, 1:2, 1:3, etc.

[0034] Furthermore, the flux is selected from one or more of ZnBr2, RbBr, V2O5, and NH4VO3.

[0035] In order to achieve the fourth objective, the present invention adopts the following technical solutions:

[0036] The present invention also provides a method for preparing the vanadium zinc rubidium bromide nonlinear optical crystal as described above, comprising the following steps:

[0037] Rb3ZnV4O 12The Br polycrystalline powder is encapsulated in a quartz tube filled with argon gas, and placed in an upper heating area of ​​a descending growth furnace. The quartz tube is rotated at a speed of 15-50 r / min, and the temperature of the upper heating area of ​​the descending growth furnace is controlled to be 380-450° C., and the temperature of the lower heating area is controlled to be 320-340° C. After constant temperature pre-burning in the upper heating area for 24-72 hours, the quartz tube is lowered at a speed of 0.2-1 cm / day to start crystal growth. After the crystal growth is completed, the vanadium zinc rubidium bromide nonlinear optical crystal is obtained;

[0038] Wherein, the crystal growth cycle is 25-40 days.

[0039] In order to achieve the fifth object, the present invention adopts the following technical solutions:

[0040] The present invention provides an application of the vanadium zinc rubidium bromide nonlinear optical crystal as described above in the preparation of laser nonlinear optical composite functional devices, electro-optical crystal devices or lasers, such as optical frequency doublers or optical parametric oscillators.

[0041] The vanadate nonlinear optical crystal of the present invention can be cut, roughly ground, polished and coated according to processing requirements to obtain the above-mentioned various optical devices.

[0042] Furthermore, the vanadium zinc rubidium bromide nonlinear optical crystal is used as a nonlinear optical crystal to generate at least one output radiation device with a frequency different from the incident electromagnetic wave after the incident electromagnetic wave containing at least one beam passes through at least one nonlinear optical crystal, wherein at least one nonlinear optical crystal is the vanadium zinc rubidium bromide nonlinear optical crystal.

[0043] The beneficial effects of the present invention are as follows:

[0044] The chemical formula of the rubidium zinc vanadate bromide nonlinear optical crystal provided by the present invention is Rb3ZnV4O 12 Br, a non-centrosymmetric structure, belongs to the orthorhombic crystal system, the space group is Cmm2, and the unit cell parameters are α=90°, β=90°, γ=90°, Z=2, It has consistent melting characteristics and can be used to prepare high-quality, large-size, transparent nonlinear optical crystals using the melt method, flux method, and crucible descent method.

[0045] The rubidium zinc vanadate bromide nonlinear optical crystal provided by the invention has the characteristics of high damage threshold, large nonlinear optical effect (about 0.7 to 1.4 times that of AGS crystal), high electro-optic coefficient, wide transmission range, stable physical and chemical properties, easy crystal growth, and the like, and is easy to cut, polish and store.

[0046] The rubidium zinc vanadate bromide nonlinear optical crystal provided by the invention can be used in preparing laser nonlinear optical composite functional devices, electro-optical crystal devices, lasers, etc., and is suitable for visible light and mid-infrared light regions. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] The specific implementation modes of the present invention are further described in detail below in conjunction with the accompanying drawings.

[0048] Figure 1 The rubidium zinc vanadate bromide Rb3ZnV4O prepared in Example 1 of the present invention is shown. 12 X-ray diffraction patterns of Br compounds.

[0049] Figure 2 The rubidium zinc vanadate bromide Rb3ZnV4O prepared in Example 1 of the present invention is shown. 12 Schematic diagram of the birefringence calculation of Br compounds.

[0050] Figure 3 The rubidium zinc vanadate bromide Rb3ZnV4O prepared in Example 2 of the present invention is shown. 12 Schematic diagram of the structure of the Br nonlinear optical crystal.

[0051] Figure 4 The rubidium zinc vanadate bromide Rb3ZnV4O in Example 2 of the present invention is shown. 12 Powder SHG diagram of Br nonlinear optical crystal measured under 2090nm laser irradiation.

[0052] Figure 5 The Rb3ZnV4O of Example 2 is shown 12 XRD comparison of Br nonlinear optical crystal powder before and after melting at 450℃.

[0053] Figure 6 The Rb3ZnV4O of Example 2 is shown 12 DSC-TG graph of Br nonlinear optical crystal.

[0054] Figure 7 The working principle diagram of a typical nonlinear optical device made of vanadium zinc rubidium bromide nonlinear optical crystal in Example 6 of the present invention is shown; wherein, 1-laser, 2-rubidium zinc vanadate bromide nonlinear optical crystal, 3-beam splitter prism.

[0055] Figure 8 The vanadium zinc bromide Rb3ZnV4O in Example 7 of the present invention is shown. 12 A working principle diagram of a typical nonlinear optical device made of Br nonlinear optical crystal; wherein: 1-laser, 2-rubidium zinc vanadate bromide nonlinear optical crystal, 3-beam splitter prism. DETAILED DESCRIPTION

[0056] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and accompanying drawings. Similar components in the accompanying drawings are represented by the same reference numerals. It should be understood by those skilled in the art that the content specifically described below is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0057] Example 1

[0058] This example provides a Rb3ZnV4O 12 The preparation method of the Br compound comprises the following steps:

[0059] It is prepared by solid phase reaction method, and the reaction equation is Rb2CO3+ZnO+2V2O5+RbBr=Rb3ZnV4O 12 Br + CO2;

[0060] The ratio of the above three reagents: Rb2CO3 (2.309 g, 0.01 mol), ZnO (0.814 g, 0.01 mol), V2O5 (3.638 g, 0.020 mol), RbBr (1.654 g, 0.01 mol);

[0061] Weigh each material according to the above dosage, put them in a mortar, add 3mL of water to grind and mix, dry at 60℃, put them into a platinum crucible, put them into a muffle furnace, heat up to 370℃ at a rate of 50℃ / h, sinter at constant temperature for 24h, and then cool naturally to obtain Rb3ZnV4O 12 Br polycrystalline powder. The comparison of its X-ray diffraction spectrum with the standard spectrum is as follows Figure 1 As shown, it shows that the XRD pattern of the prepared polycrystalline powder is basically consistent with the theoretical XRD pattern.

[0062] Figure 2 The rubidium zinc vanadate bromide Rb3ZnV4O 12 Schematic diagram of the birefringence calculation of Br compounds. It can be seen from the figure that the birefringence of the crystal can reach 0.06 in the range of 1-5μm, which is sufficient to achieve phase matching.

[0063] Example 2

[0064] Preparation of Rb3ZnV4O by melt method 12 Br nonlinear optical crystal, comprising the following steps:

[0065] Weigh 420.73g of synthesized Rb3ZnV4O 12Br polycrystalline powder (0.5 mol) was ground and mixed in a mortar, melted in batches in a muffle furnace and loaded into a Φ80 mm×80 mm crucible; the crucible after melting was placed in a vertical crystal growth furnace, heated to 400°C, stirred at a constant temperature for 48 hours, and then cooled to 5°C above the saturation point, seed crystals were introduced, and the temperature was reduced at a rate of 0.5°C / day. At the same time, the seed crystal rod was rotated at a speed of 10r / min to start crystal growth. After the crystal growth was completed, the seed crystal rod was lifted to lift the crystal from the liquid surface, and then the temperature was reduced to room temperature at a rate of 20°C / h to obtain transparent Rb3ZnV4O 12 Br nonlinear optical crystal, referred to as RZVB, the total growth period is 30 days, the resulting crystal size is 12×22×10mm 3 The schematic diagram of the obtained crystal structure is shown in Figure 3 shown.

[0066] Figure 4 Showing different particle sizes of zinc vanadate bromide Rb3ZnV4O 12 The powder frequency spectrum of Br powder measured under 2090nm laser irradiation, Rb3ZnV4O under laser irradiation 12 The frequency doubling effect of Br is about 0.7-1.4 times that of AGS.

[0067] Figure 5 It is shown that the Rb3ZnV4O 12 The XRD patterns of Br nonlinear optical crystal powder before and after melting at 450°C were compared, indicating that the powder is the same compound before and after melting.

[0068] Figure 6 It shows that Rb3ZnV4O 12 DSC-TG diagram of Br nonlinear optical crystal. The test condition is 5℃ / min. It can be seen that the crystal has consistent melting properties and no volatility before 500℃.

[0069] Example 3

[0070] Preparation of Rb3ZnV4O by co-solvent method 12 Br nonlinear optical crystal, comprising the following steps:

[0071] RbBr was used as flux and the molar ratio of polycrystalline powder to flux was 1:2. 420.73 g of synthesized Rb3ZnV4O 12Br polycrystalline powder (0.5 mol) and 165 g RbBr (1 mol) were ground and mixed in a mortar, melted in batches and loaded into a Φ80 mm × 80 mm crucible; the crucible after the melting was placed in a vertical crystal growth furnace, heated to 400 ° C, stirred at a constant temperature for 48 hours, and then cooled to 5 ° C above the saturation point, seed crystals were introduced, and the temperature was reduced at a rate of 0.5 ° C / day, and the seed crystal rod was rotated at a speed of 10 r / min to start crystal growth. After the crystal growth was completed, the crystal was lifted from the liquid surface, and then cooled to room temperature at a rate of 20 ° C / h, and transparent Rb3ZnV4O 12 Br nonlinear optical crystal, the total growth period is 30 days, the resulting crystal size is 11×20×9mm 3 .

[0072] Example 4

[0073] Preparation of Rb3ZnV4O by crucible descent method 12 Br nonlinear optical crystal, comprising the following steps:

[0074] Weigh 420.73g of synthesized Rb3ZnV4O 12 Br polycrystalline powder (0.5 mol) was ground and mixed in a mortar, melted in batches in a muffle furnace and loaded into a Φ20 mm × 180 mm quartz tube, which was filled with argon and then packaged; the packaged quartz tube was placed in a descending crystal growth furnace, and the temperature of the upper heating area of ​​the descending growth furnace was controlled to be 390 ° C, and the temperature of the lower heating area was controlled to be 340 ° C. After constant temperature rotation for 48 hours, it was descended at a rate of 0.5 cm / day and a rotation speed of 10 r / min. After the crystal growth was completed, the crystal was taken out from the quartz tube to obtain transparent Rb3ZnV4O 12 Br nonlinear optical crystal, the total growth period is 35 days, the resulting crystal size is 16×22×14mm 3 .

[0075] Example 5

[0076] This example provides a Rb3ZnV4O 12 The preparation method of Br nonlinear crystal comprises the following steps:

[0077] It is prepared by hydrothermal method, and the reaction equation is Rb2CO3+ZnO+2V2O5+RbBr=Rb3ZnV4O 12 Br + CO2;

[0078] The ratio of the above three reagents: Rb2CO3 (4.618g, 0.02mol), ZnO (1.628g, 0.02mol), V2O5 (7.276g, 0.04mol), RbBr (3.308g, 0.02mol);

[0079] Weigh the reagents according to the above dosages, put them in a mortar, grind and mix them thoroughly, put them into a 100mL hydrothermal reactor, add 30mL deionized water, heat to 200℃ at a rate of 50℃ / h for hydrothermal reaction, keep warm for 24h, then cool to room temperature at a rate of 10℃ / day to obtain Rb3ZnV4O 12 Br nonlinear crystal.

[0080] Example 6

[0081] This example provides a Rb3ZnV4O 12 Nonlinear optical devices prepared from Br crystals:

[0082] Rb3ZnV4O 12 The Br crystal is cut into a Rb3ZnV4O with a cross-sectional size of 3×3 mm and a length of 10 mm in the light direction. 12 Br crystal device, the light-transmitting surfaces at both ends are precisely polished and coated. Figure 7 As shown, the crystal device is placed in Figure 7 At the position of the middle mark 2, a 1064nm Q-switched Nd:YAG laser is used as the light source, which can output a green laser with a wavelength of 532nm.

[0083] Example 7

[0084] This example provides a Rb3ZnV4O 12 Nonlinear optical devices prepared from Br crystals:

[0085] Rb3ZnV4O 12 The Br crystal is cut into a Rb3ZnV4O with a cross-sectional size of 3×3 mm and a length of 10 mm in the light direction. 12 Br crystal device, the light-transmitting surfaces at both ends are precisely polished and coated. Figure 8 As shown, the crystal device is placed in Figure 8 At the position of the middle mark 2, a 1064nm Q-switched Nd:YAG laser is used as the light source, which can output infrared light with a wavelength of 3-5 microns.

[0086] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. A homogeneous molten halogen vanadate compound, characterized in that: The chemical formula of the vanadate compound is Rb3ZnV4O 12 Br.

2. A method for preparing a vanadate compound as claimed in claim 1, characterized in that: The vanadate compound is prepared by a high temperature solid phase synthesis method or a hydrothermal method; The solid phase synthesis method comprises the following steps: The Rb-containing compound, Zn-containing compound, V-containing compound and Br-containing compound are ground and mixed, and the temperature is raised to 320-370°C at a rate of 10-50°C / h, and sintered at a constant temperature for 24-72h to obtain Rb3ZnV4O 12 Br polycrystalline powder; The hydrothermal method comprises the following steps: The Rb-containing compound, Zn-containing compound, V-containing compound and Br-containing compound are ground and mixed, and then put into a hydrothermal reactor, and water is added. The temperature is raised to 180-200°C at a rate of 10-50°C / h, and the temperature is kept constant for 24-72h, and then the temperature is lowered to room temperature at a rate of 10-50°C / day to obtain Rb3ZnV4O 12 Br polycrystalline powder.

3. The preparation method according to claim 2, characterized in that: The Rb-containing compound is selected from one or more of Rb oxides, Rb hydroxides, Rb carbonates, Rb halides, Rb nitrates and Rb oxalates; The Zn-containing compound is selected from one or more of Zn oxides, Zn hydroxides, Zn carbonates, Zn halides, Zn nitrates and Zn oxalates; The V-containing compound is selected from one or more of V oxides, V hydroxides, V halides, V nitrates, V oxalates and ammonium vanadates; The Br-containing compound is selected from one or more of Br rubidium salt, Br zinc salt and Br vanadium salt.

4. The preparation method according to claim 2, characterized in that: The molar ratio of the elements Rb, Zn, V and Br in the Rb-containing compound, the Zn-containing compound, the V-containing compound and the Br-containing compound is 3:1:4:

1.

5. A vanadium zinc rubidium bromide nonlinear optical crystal, characterized in that: The chemical formula of the vanadium zinc rubidium bromide nonlinear optical crystal is Rb3ZnV4O 12 Br, a non-centrosymmetric structure, belongs to the orthorhombic crystal system, the space group is Cmm2, and the unit cell parameters are α=90°, β=90°, γ=90°, Z=2, 6. A method for preparing the vanadium zinc rubidium bromide nonlinear optical crystal as claimed in claim 5, characterized in that: The steps include: Putting the crystal growth material into a crystal growth furnace, heating it to 370-450° C. to obtain a melt, stirring it at a constant temperature for 24-72 hours, cooling it to 1-10° C. above the melt saturation point temperature and introducing a seed crystal, cooling it at a rate of 0.1-5° C. / day, and rotating the seed crystal rod at a rate of 10-50 r / min at the same time to start crystal growth, after the crystal growth is completed, lifting the crystal from the liquid surface, and then annealing it to room temperature at a cooling rate of no more than 100° C. / h to obtain the vanadium zinc rubidium bromide nonlinear optical crystal; Wherein, the crystal growth cycle is 25-40 days.

7. The preparation method according to claim 6, characterized in that: The crystal growth material is selected from Rb3ZnV4O 12 Br polycrystalline powder or Rb3ZnV4O 12 A mixture of Br polycrystalline powder and flux; Preferably, the Rb3ZnV4O 12 The molar ratio of Br polycrystalline powder to flux is 1:1-3.

8. The preparation method according to claim 7, characterized in that: The flux is selected from one or more of ZnBr2, RbBr, V2O5, and NH4VO3.

9. A method for preparing the vanadium zinc rubidium bromide nonlinear optical crystal as claimed in claim 5, characterized in that: The steps include: Rb3ZnV4O 12 The Br polycrystalline powder is encapsulated in a quartz tube filled with argon gas, and placed in an upper heating area of ​​a descending growth furnace. The quartz tube is rotated at a speed of 15-50 r / min, and the temperature of the upper heating area of ​​the descending growth furnace is controlled to be 380-450° C., and the temperature of the lower heating area is controlled to be 320-340° C. After constant temperature pre-burning in the upper heating area for 24-72 hours, the quartz tube is lowered at a speed of 0.2-1 cm / day to start crystal growth. After the crystal growth is completed, the vanadium zinc rubidium bromide nonlinear optical crystal is obtained; Wherein, the crystal growth cycle is 25-40 days.

10. Use of the vanadium zinc rubidium bromide nonlinear optical crystal as claimed in claim 5 in the preparation of laser nonlinear optical composite functional devices, electro-optical crystal devices or lasers.

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