Preparation method and application of compound rubidium antimony aluminum silicate and nonlinear optical crystal

Abstract

The invention discloses a compound rubidium antimony aluminum silicate and a preparation method and application of a rubidium antimony aluminum silicate nonlinear optical crystal, the chemical formula of the compound rubidium antimony aluminum silicate and the crystal of the compound rubidium antimony aluminum silicate is Rb5Sb4AlSi4O22, the crystal belongs to an orthorhombic system, the space group is that the cell parameter Z is 2, and the molecular weight is 1405.67. The compound rubidium antimony aluminum silicate is synthesized by adopting a high-temperature solid-phase reaction method, the rubidium antimony aluminum silicate nonlinear optical crystal grows by adopting a high-temperature solution method, the preparation method is simple, convenient and low in cost, and the obtained crystal has the advantages of wide light transmission range, stable physical and chemical properties, easiness in storage and the like, and can be used for preparing nonlinear optical devices.

Description

Technical Field

[0001] The present invention relates to a 22 The invention relates to a compound of rubidium antimony aluminum silicate and a rubidium antimony aluminum silicate nonlinear optical crystal, a method for preparing the crystal and a nonlinear optical device made using the crystal. Background Art

[0002] With the rapid development of laser technology, it has shown important application value in the fields of precision machining, biomedicine, communication detection, etc. In order to achieve multi-band and high-efficiency laser output, the use of nonlinear optical (NLO) crystals for frequency conversion has become a key means. Nonlinear optical crystals can extend the laser wavelength to the ultraviolet region, near-infrared region and even mid-to-far infrared region that are invisible to the human eye through processes such as frequency doubling, sum frequency and difference frequency. They are indispensable core functional materials in modern optoelectronic devices. Traditional NLO crystals such as β-BaB2O4 (BBO), LiB3O5 (LBO), CsB3O5 (CBO), CsLiB6O 10 (CLBO), KBe2BO3F2 (KBBF), KH2PO4 (KDP), KTiOPO4 (KTP), etc. are widely used due to their good nonlinear optical response and transmission range. However, they generally suffer from low nonlinear optical coefficients, unsatisfactory UV cutoff edges, poor thermal and environmental stability, and other issues, making it difficult to meet the increasingly complex and demanding application requirements. Therefore, the development of a new generation of NLO crystals with large nonlinear optical coefficients, wide transmission bands, and excellent thermal stability has become a hot topic in current research.

[0003] In recent years, researchers have turned their attention to oxide crystal systems with diverse structures and flexible configurations, especially compounds with tetrahedral groups. Studies have shown that tetrahedral structural units with directional electronic structures such as [SiO4] and [AlO4] have significant advantages in constructing non-centrosymmetric crystal structures. Silicates play an important role in the field of materials science due to their rich mineral resources and structural diversity. Their basic structural unit is the [SiO4] tetrahedron, which can form framework structures of various dimensions through different connection methods, giving the material excellent chemical stability and design flexibility. In the study of nonlinear optical materials, although traditional silicate crystals have received less attention due to their intrinsic centrosymmetry or small nonlinear optical coefficients, recent studies have shown that the nonlinear optical response of silicate materials can be effectively stimulated by the reasonable introduction of structural units and metal cations with non-centrosymmetric characteristics. Some alkali metals (such as Li+, Na + etc.) and alkaline earth metals (such as Ba 2 + 、Sr 2+ 、Be 2+Silicate compounds are found to have strong SHG effect and good UV transmittance. For example, Li2BaSiO4 has a SHG response of 2.8xKDP, with a UV cutoff edge shorter than 190 nm, which is attributed to the strong polarization effect from the unique edge-sharing [LiO4] and [SiO4] tetrahedral coordination. First-principles calculations show that the non-centrosymmetrically arranged tetrahedral units in the Li2BaSiO4 structure are the main source of its large SHG effect (Hongping Wu, Bingbing Zhang, Hongwei Yu, Zhanggui Hu, Jiyang Wang, Yicheng Wu, P. Shiv Halasyamani, Designing Silicates as Deep-UV Nonlinear Optical (NLO) Materials using Edge-Sharing Tetrahedra, Angewandte Chemie-international Edition, 2020, 132, 9007-9011.). In addition, the UV cutoff edges of Na2BeSiO4 and Li2BeSiO4 are 173 nm and 162 nm, respectively, and their SHG responses are 0.6xKDP and 1.6xKDP, respectively (YiGang Chen, Xingxing Jiang, HongXiao Lv, Dajiang Mei, Xia Zhang, Yao Guo, Zheshuai Lin, XianMing Zhang, Two α-SiO2-Related Deep-Ultraviolet Phase-Matchable Optical Nonlinear Beryllium Silicate Crystals Na2BeSiO4 and Li2BeSiO4 with Enhanced SHG Effect, Small, 2024, 2408360.), and first-principles calculations show that the large SHG response is mainly due to the distortion and uniform arrangement of the [SiO4] tetrahedral units.

[0004] In summary, in the synthesis of new silicate nonlinear optical crystals, the introduction of alkali metals and alkaline earth metals not only helps to build non-centrosymmetric crystal structures, but also can obtain a short UV cutoff edge. At the same time, the [SiO4] group with tetrahedral structure is also conducive to generating a short UV cutoff edge. Therefore, the synergistic effect between alkali metal and alkaline earth metal cations and [SiO4], [AlO4] and other tetrahedral groups is expected to significantly improve the possibility of obtaining high-performance silicate nonlinear optical crystals. SUMMARY

[0005] The first object of the present invention is to provide a compound rubidium antimony aluminum silicate and a nonlinear optical crystal, the chemical formula of which is Rb5Sb4AlSi4O 22 .

[0006] The second object of the present invention is to provide a preparation method for synthesizing the compound rubidium antimony aluminum silicate by a high-temperature solid-phase reaction method and growing the rubidium antimony aluminum silicate nonlinear optical crystal by a high-temperature solution method.

[0007] The third object of the present invention is to provide the use of rubidium antimony aluminum silicate nonlinear optical crystals for preparing nonlinear optical devices such as frequency doubling generators, frequency converters or optical parametric oscillators.

[0008] The technical solutions for achieving the above objectives are as follows:

[0009] The compound rubidium antimony aluminum silicate provided by the present invention has the chemical formula Rb5Sb4AlSi4O 22 The preparation method of the compound is to uniformly mix and fully grind the raw materials containing rubidium, antimony, aluminum and silicon according to the stoichiometric ratio, place them in a muffle furnace, pre-sinter at low temperature to remove the gas in the raw materials, and then heat and calcine for several days, taking them out and grinding them several times during the period, and finally obtaining the pure phase of the compound rubidium antimony aluminum silicate;

[0010] The rubidium-containing compound is at least one of rubidium oxide, rubidium hydroxide or a rubidium salt; the rubidium salt includes at least one of rubidium chloride, rubidium bromide, rubidium nitrate, rubidium carbonate and rubidium sulfate;

[0011] The antimony-containing compound is at least one of antimony oxide, antimony hydroxide or antimony salt; the antimony salt includes at least one of antimony chloride and antimony sulfate;

[0012] The aluminum-containing compound is at least one of aluminum oxide or aluminum salt; the aluminum salt includes at least one of aluminum chloride, aluminum bromide, aluminum nitrate, and aluminum sulfate;

[0013] The silicon-containing compound is at least one of silicon oxide or silicon salt; the silicon salt includes at least one of silicon chloride and silicon bromide.

[0014] The rubidium antimony aluminum silicate compound is prepared by a high-temperature solid-phase reaction method according to the following chemical reaction formula:

[0015] 1)5Rb2CO3+4Sb2O4+Al2O3+8SiO2+2O2→2Rb5Sb4AlSi4O 22 +5CO2

[0016] 2)5Rb2O+4Sb2O4+Al2O3+8SiO2+2O2→2Rb5Sb4AlSi4O 22

[0017] 3)10RbOH+4Sb2O4+Al2O3+8SiO2+2O2→2Rb5Sb4AlSi4O 22 +5H2O

[0018] 4)20RbCl+8Sb2O4+2Al2O3+16SiO2+9O2→4Rb5Sb4AlSi4O 22 +10Cl2

[0019] 5)20RbBr+8Sb2O4+2Al2O3+16SiO2+9O2→4Rb5Sb4AlSi4O 22 +10Br2

[0020] 6)20RbNO3+8Sb2O4+2Al2O3+16SiO2→4Rb5Sb4AlSi4O 22 +20NO2↑+O2↑

[0021] 7)10Rb2SO4+8Sb2O4+2Al2O3+16SiO2→4Rb5Sb4AlSi4O 22 +10SO2↑+O2↑

[0022] 8)5Rb2CO3+4Sb2O3+Al2O3+8SiO2+4O2→2Rb5Sb4AlSi4O 22 +5CO2

[0023] 9)5Rb2CO3+4Sb2O5+Al2O3+8SiO2→2Rb5Sb4AlSi4O 22 +5CO2↑

[0024] 10)5Rb2CO3+8Sb(OH)3+Al2O3+8SiO2+4O2→2Rb5Sb4AlSi4O 22 +12H2O

[0025] 11)5Rb2CO3+8SbCl3+Al2O3+8SiO2+10O2→2Rb5Sb4AlSi4O 22 +5CO2+12Cl2

[0026] 12)5Rb2CO3+4Sb2(SO4)3+Al2O3+8SiO2→2Rb5Sb4AlSi4O 22 +5CO2↑+4SO2↑+15O2↑

[0027] 13)10Rb2CO3+8Sb2O4+4AlCl3+16SiO2+7O2→4Rb5Sb4AlSi4O22 +10CO2+6Cl2

[0028] 14)10Rb2CO3+8Sb2O4+4AlBr3+16SiO2+7O2→4Rb5Sb4AlSi4O 22 +10CO2+6Br2

[0029] 15)10Rb2CO3+8Sb2O4+4Al(NO3)3+16SiO2+O2→4Rb5Sb4AlSi4O 22 +10CO2+

[0030] 12NO2

[0031] 16)10Rb2CO3+8Sb2O4+2Al2(SO4)3+16SiO2+O2→4Rb5Sb4AlSi4O 22 +10CO2+6SO2

[0032] 17)5Rb2CO3+4Sb2O4+Al2O3+8SiCl4+10O2→2Rb5Sb4AlSi4O 22 +5CO2+16Cl2

[0033] 18)5Rb2CO3+4Sb2O4+Al2O3+8SiBr4+10O2→2Rb5Sb4AlSi4O 22 +5CO2+16Br2

[0034] The present invention provides a rubidium antimony aluminum silicate nonlinear optical crystal, the chemical formula of which is Rb5Sb4AlSi4O 22 , its molecular weight is 1405.67, the crystal has a non-centrosymmetric structure, belongs to the orthorhombic system, and the space group is I4 _ m2, the unit cell parameters are Z=2, band gap is 4.59eV, and ultraviolet cutoff edge is at 270nm.

[0035] The present invention provides a method for preparing a rubidium antimony aluminum silicate nonlinear optical crystal, which uses a high-temperature solution method to grow the rubidium antimony aluminum silicate nonlinear optical crystal. The specific growth steps are as follows:

[0036] a. mixing the compound of rubidium antimony aluminum silicate single-phase polycrystalline powder with a fluxing agent uniformly, heating to 900-1100℃ at a heating rate of 10-100℃ / h, keeping the temperature for not less than 48h, cooling the mixed solution to 750-900℃, wherein the molar ratio of the compound of rubidium antimony aluminum silicate single-phase polycrystalline powder to the fluxing agent is 1:0-20; or directly mixing a mixture containing a rubidium-containing compound, an antimony-containing compound, an aluminum-containing compound and a silicon-containing compound or a mixture containing a rubidium-containing compound, an antimony-containing compound, an aluminum-containing compound, a silicon-containing compound and a fluxing agent, heating to 900-1100℃ at a heating rate of 10-100℃ / h, keeping the temperature for not less than 48h, cooling the mixed solution to 700-900℃, wherein the molar ratio of the rubidium-containing compound, the antimony-containing compound, the aluminum-containing compound and the silicon-containing compound to the fluxing agent is 4.7-5.3:3.7-4.3:0.7-1.3:3.7-4.3:0-20.

[0037] The fluxing agent used mainly includes various potassium salt substances, such as potassium oxide (K2O), potassium fluoride (KF), lead oxide (PbO), lead fluoride (PbF2), molybdenum trioxide (MoO3) and bismuth oxide (Bi2O3). In addition, some composite fluxing agents combined from the above components are also commonly used, for example, K2O-PbO, KF-PbF2, KF-MoO3, K2O-MoO3, K2O-Bi2O3, PbO-MoO3, or one or more combinations of three-component systems such as PbO-MoO3-K2O.

[0038] The compound of rubidium antimony aluminum silicate single-phase polycrystalline powder in this step is prepared by a high-temperature solid-phase reaction method, including the following steps: mixing a rubidium-containing compound, an antimony-containing compound, an aluminum-containing compound and a silicon-containing compound uniformly, wherein the molar ratio of rubidium element in the rubidium-containing compound, antimony element in the antimony-containing compound, aluminum element in the aluminum-containing compound and silicon element in the silicon-containing compound is 4.7-5.3:3.7-4.3:0.7-1.3:3.7-4.3, grinding and then placing in a muffle furnace for calcination at 400℃, the calcination time being not less than 5h to remove the gas in the raw materials, then sintering at 950-1050℃, the calcination time being not less than 48h, taking out and grinding multiple times during the period, and finally cooling to room temperature to obtain the compound of rubidium antimony aluminum silicate single-phase polycrystalline powder.

[0039] b. preparing a rubidium antimony aluminum silicate seed crystal: slowly cooling the mixed solution obtained in step a to room temperature at a cooling rate of 1-5℃ / h to obtain a rubidium antimony aluminum silicate seed crystal by spontaneous crystallization;

[0040] c. Put the Pt crucible containing the mixed solution prepared in step a into a crystal growth furnace, fix the seed crystal obtained in step b on a seed crystal rod, lower the seed crystal from the top of the crystal growth furnace, preheat the seed crystal for 2-4 h, lower the seed crystal to contact the surface of the mixed solution at a temperature 2-10 DEG C higher than the saturation point, keep the temperature constant for 1-2 h to eliminate impurities on the surface of the seed crystal, and then lower the temperature to the saturation point at a rate of 1-10 DEG C / min;

[0041] d. Slowly lower the temperature at a rate of 1-3 DEG C / day, grow the crystal at a seed crystal rod rotation speed of 5-50 rpm, when the crystal grows to the required size, lift the crystal to 1-2 cm above the liquid surface, then lower the temperature to room temperature at a rate of 10-50 DEG C / h, finally open the furnace and take out the crystal to obtain the rubidium antimony aluminum silicate nonlinear optical crystal.

[0042] In the composite fluxing agent system, the molar ratio ranges of the components are as follows: in the K2O-PbO system, the molar ratio of K2O to PbO is 1-4:2-7; in the KF-PbF2 system, the molar ratio of KF to PbF2 is 1-9:1-5; in the KF-MoO3 system, the molar ratio of KF to MoO3 is 2-8:1-5; in the K2O-MoO3 system, the molar ratio of K2O to MoO3 is 1-3:2-5; in the K2O-Bi2O3 system, the molar ratio of K2O to Bi2O3 is 1-7:1-5; in the PbO-MoO3 system, the molar ratio of PbO to MoO3 is 1-3:2-6; and in the ternary system PbO-MoO3-K2O, the molar ratio of the three components is 1-3:2-4:2-8. These ratio ranges help to regulate the performance of the fluxing agent to adapt to different crystal growth conditions.

[0043] In the growth process of the rubidium antimony aluminum silicate nonlinear optical crystal, various fluxing agents are introduced, including potassium oxide (K2O), potassium fluoride (KF), lead oxide (PbO), lead fluoride (PbF2), molybdenum trioxide (MoO3) and bismuth oxide (Bi2O3). Meanwhile, a composite fluxing agent composed of these components is also used, such as one of K2O-PbO, KF-PbF2, KF-MoO3, K2O-MoO3, K2O-Bi2O3, PbO-MoO3 or PbO-MoO3-K2O, which helps to promote the effective nucleation and growth of the target crystal, so that a larger crystal sample is obtained. The grown crystal not only has excellent thermal stability, but also has a wide optical transmission range and good physical and chemical stability, showing good application prospects.

[0044] The rubidium antimony aluminum silicate crystal obtained by the method has application value as a nonlinear optical crystal in a full solid-state laser for making a frequency doubling generator, a frequency converter and an optical parametric oscillator according to the requirements of device application. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 The present invention Rb5Sb4AlSi4O 22 X-ray diffraction pattern of powder.

[0046] Figure 2 The present invention Rb5Sb4AlSi4O 22 UV-Vis-NIR diffuse reflectance spectrum of the powder.

[0047] Figure 3 The present invention Rb5Sb4AlSi4O 22 Unit cell structure diagram.

[0048] Figure 4 The present invention Rb5Sb4AlSi4O 22 Schematic diagram of the working principle of nonlinear optical devices made of crystals, where 1 is the laser, 2 is the incident laser beam, and 3 is Rb5Sb4AlSi4O 22 The crystal, 4 is the generated laser beam, and 5 is the filter. DETAILED DESCRIPTION

[0049] The present invention will be described in detail below with reference to the accompanying drawings and embodiments, but is not limited to the embodiments described. Any improvements and variations made on the basis of the present invention are within the scope of protection of the present invention.

[0050] Example 1:

[0051] According to the reaction formula: 5Rb2CO3+4Sb2O4+Al2O3+8SiO2+2O2→2Rb5Sb4AlSi4O 22 +5CO2 synthesis compound Rb5Sb4AlSi4O 22 .

[0052] Rb2CO3, Sb2O4, Al2O3, and SiO2 were weighed in a molar ratio of 5:4:1:8 and put into a mortar, mixed and ground, then placed into an open corundum crucible of Φ100mm×100mm, placed in a muffle furnace, slowly heated to 400℃ and calcined, kept at a constant temperature for 10h to remove gas, then heated to 800℃ and calcined for 24h, taken out and ground, then placed in a muffle furnace, and heated to 1050℃ and calcined for not less than 72h to prepare a single-phase polycrystalline powder of rubidium antimony aluminum silicate. The powder X-ray diffraction test and analysis showed that the powder X-ray diffraction spectrum of the obtained sample was consistent with the attached Figure 1 The X-ray diffraction patterns are consistent;

[0053] The prepared compound rubidium antimony aluminum silicate Rb5Sb4AlSi4O 22The single-phase polycrystalline powder was mixed with a flux K2O-PbO in a molar ratio of 1:2, wherein the molar ratio of K2O:PbO was 4:1, and placed in a Φ60mm×60mm platinum crucible. The temperature was raised to 1010°C and kept constant for at least 48 hours to allow the solution to mix uniformly. A Pt wire was then added, and the temperature was then lowered to induce spontaneous crystallization.

[0054] Slowly cooling the solution at a cooling rate of 1-5°C / h to obtain rubidium antimony aluminum silicate seed crystals;

[0055] Growing crystals in compound solutions: Spontaneously crystallized Rb5Sb4AlSi4O 22 Small crystals are used as seed crystals. Platinum wire is used to fix the seed crystals on the seed crystal rod. The seed crystals are first placed 1-2 cm above the liquid surface for preheating. Then, when the temperature is 2-10°C higher than the saturation point, the seed crystals are immersed below the liquid surface and kept at a constant temperature for 1-2 hours to remove impurities on the seed crystal surface. Then, the temperature is quickly cooled to the saturation point temperature.

[0056] Then cool down at a rate of 1-3℃ / day, and the seed rod speed is 5-50rpm. After the growth is completed, the crystal is lifted 1-2cm above the liquid surface, and cooled to room temperature at a rate of 10-50℃ / h. Then the crystal is taken out to obtain Rb5Sb4AlSi4O 22 crystal.

[0057] The raw material rubidium carbonate in the reaction formula can be replaced by other rubidium salts such as rubidium oxide, rubidium hydroxide, rubidium chloride, rubidium bromide, rubidium nitrate, or rubidium sulfate, antimony oxide can be replaced by other antimony salts, aluminum oxide can be replaced by other aluminum salts, and silicon oxide can be replaced by other silicates.

[0058] Example 2:

[0059] According to the reaction formula: 20RbCl+8Sb2O4+2Al2O3+16SiO2+9O2→4Rb5Sb4AlSi4O 22 +10Cl2 to synthesize the compound Rb5Sb4AlSi4O 22 .

[0060] RbCl, Sb2O4, Al2O3, and SiO2 were weighed in a molar ratio of 20:8:2:16 and put into a mortar, mixed and ground, then placed into an open corundum crucible of Φ100mm×100mm, placed in a muffle furnace, slowly heated to 400℃ and calcined, kept at a constant temperature for 24h to remove gas, then heated to 750℃ and calcined for 24h, taken out and ground, then placed in a muffle furnace, and heated to 950℃ and calcined for not less than 48h to prepare a single-phase polycrystalline powder of rubidium antimony aluminum silicate. The powder X-ray diffraction test and analysis showed that the powder X-ray diffraction spectrum of the obtained sample was consistent with the attached Figure 1 The X-ray diffraction patterns are consistent;

[0061] The prepared compound rubidium antimony aluminum silicate Rb5Sb4AlSi4O 22 The single-phase polycrystalline powder is mixed with a flux KF-PbF2 at a molar ratio of 1:4, wherein the molar ratio of KF to PbF2 is 4:1, and is loaded into a Φ60 mm*60 mm platinum-gold crucible, and is heated to a temperature of 1050°C, and is kept at the temperature for not less than 48 h, so that the solution is uniformly mixed, and then a Pt wire is lowered into the solution, and then the solution is cooled to induce spontaneous crystallization;

[0062] The solution is slowly cooled at a cooling rate of 1-5°C / h, and a rubidium antimony aluminum silicate seed crystal is obtained;

[0063] The compound solution is used for growing a crystal: the Rb5Sb4AlSi4O 22 Small grains are used as seed crystals, and the seed crystals are fixed on a seed crystal rod by using a platinum-gold wire, the seed crystals are first placed at a position 1-2 cm above the liquid surface for preheating treatment, and then the seed crystals are immersed below the liquid surface at a temperature 2-10°C higher than the saturation point temperature, and are kept at the temperature for 1-2 h to remove impurities on the surface of the seed crystals, and then the temperature is quickly reduced to the saturation point temperature;

[0064] Then the temperature is reduced at a rate of 1-3°C / d, and the rotation speed of the seed crystal rod is 5-50 rpm, after the growth is completed, the crystal is lifted to a position 1-2 cm above the liquid surface, and is reduced to room temperature at a rate of 10-50°C / h, and then the crystal is taken out, and a Rb5Sb4AlSi4O 22 crystal is obtained.

[0065] The raw material rubidium chloride in the reaction formula can be replaced by rubidium oxide or rubidium hydroxide or rubidium carbonate or rubidium bromide or rubidium nitrate or rubidium sulfate or other rubidium salts, the antimony oxide can be replaced by other antimony salts, the aluminum oxide can be replaced by other aluminum salts, and the silicon oxide can be replaced by other silicates.

[0066] Example 3:

[0067] According to the reaction formula: 5Rb2O+4Sb2O4+Al2O3+8SiO2+2O2→2Rb5Sb4AlSi4O 22 The compound Rb5Sb4AlSi4O 22 .

[0068] Rb2O, Sb2O4, Al2O3, SiO2 are weighed according to the molar ratio of 5:4:1:8, put into a mortar, mixed and ground, then put into a Φ100mm*100mm open corundum crucible, placed in a muffle furnace, slowly heated to 400℃, calcined for 24h to remove gas, then heated to 750℃, calcined for 24h, then taken out and ground, then put into a muffle furnace, heated to 1020℃, calcined for not less than 48h to prepare a single-phase polycrystalline powder of the compound rubidium antimony aluminum silicate. The obtained sample is analyzed by powder X-ray diffraction, and the powder X-ray diffraction spectrum of the sample is consistent with the X-ray diffraction spectrum of the compound rubidium antimony aluminum silicate Rb5Sb4AlSi4O Figure 1 attached figure.

[0069] The prepared compound rubidium antimony aluminum silicate Rb5Sb4AlSi4O 22 The single-phase polycrystalline powder is mixed with a flux KF-MoO3 according to a molar ratio of 1:4, wherein the molar ratio of KF to MoO3 is 4:1, and is loaded into a Φ60mm*60mm platinum-gold crucible, heated to a temperature of 1000℃, and kept at a constant temperature for not less than 48h to make the solution uniform, and then a Pt wire is lowered into the solution, and then the solution is induced to spontaneously crystallize by cooling.

[0070] The solution is slowly cooled at a cooling rate of 1-5℃ / h to obtain a lithium barium gallium silicate seed crystal.

[0071] Growth of a crystal in a compound solution: the Rb5Sb4AlSi4O 22 Small crystal grains are used as seed crystals, and the seed crystals are fixed on a seed crystal rod by a platinum-gold wire. The seed crystals are first placed 1-2cm above the liquid surface for preheating treatment, and then the seed crystals are immersed below the liquid surface at a temperature of 2-10℃ higher than the saturation point temperature, and kept at a constant temperature for 1-2h to remove impurities on the surface of the seed crystals, and then the solution is quickly cooled to the saturation point temperature.

[0072] Then the solution is cooled at a rate of 1-3℃ / day, and the seed crystal rod rotates at a speed of 5-50rpm. After the growth is completed, the crystal is lifted 1-2cm above the liquid surface, and then cooled to room temperature at a rate of 10-50℃ / h. Then the crystal is taken out, and a Rb5Sb4AlSi4O 22 crystal is obtained.

[0073] The raw material rubidium oxide in the reaction formula can be replaced by rubidium chloride, rubidium hydroxide, rubidium carbonate, rubidium bromide, rubidium nitrate or other rubidium salts, antimony oxide can be replaced by other antimony salts, aluminum oxide can be replaced by other aluminum salts, and silicon oxide can be replaced by other silicates.

[0074] Example 4:

[0075] According to the reaction formula: 5Rb2CO3+4Sb2O3+Al2O3+8SiO2+4O2→2Rb5Sb4AlSi4O 22+5CO2 synthesis compound Rb5Sb4AlSi4O 22 .

[0076] Rb2CO3, Sb2O3, Al2O3, and SiO2 were weighed in a molar ratio of 5:4:1:8 and put into a mortar, mixed and ground, then placed into an open corundum crucible of Φ100mm×100mm, placed in a muffle furnace, slowly heated to 400℃ and calcined, kept at a constant temperature for 24h to remove gas, then heated to 750℃ and calcined for 24h, taken out and ground, then placed in a muffle furnace, and heated to 1000℃ and calcined for not less than 48h to prepare a single-phase polycrystalline powder of rubidium antimony aluminum silicate. The powder X-ray diffraction test and analysis showed that the powder X-ray diffraction spectrum of the obtained sample was consistent with the attached Figure 1 The X-ray diffraction patterns are consistent;

[0077] The prepared compound rubidium antimony aluminum silicate Rb5Sb4AlSi4O 22 The single-phase polycrystalline powder was mixed with a flux K2O-Bi2O3 in a molar ratio of 1:3, wherein the molar ratio of K2O to Bi2O3 was 4:1, and placed in a Φ60mm×60mm platinum crucible. The temperature was raised to 950°C and kept constant for at least 48 hours to allow the solution to be uniformly mixed. A Pt wire was then added, and the temperature was then lowered to induce spontaneous crystallization.

[0078] Slowly cooling the solution at a cooling rate of 1-5°C / h to obtain rubidium antimony aluminum silicate seed crystals;

[0079] Growing crystals in compound solutions: Spontaneously crystallized Rb5Sb4AlSi4O 22 Small crystals are used as seed crystals. Platinum wire is used to fix the seed crystals on the seed crystal rod. The seed crystals are first placed 1-2 cm above the liquid surface for preheating. Then, when the temperature is 2-10°C higher than the saturation point, the seed crystals are immersed below the liquid surface and kept at a constant temperature for 1-2 hours to remove impurities on the seed crystal surface. Then, the temperature is quickly cooled to the saturation point temperature.

[0080] Then cool down at a rate of 1-3℃ / day, and the seed rod speed is 5-50rpm. After the growth is completed, the crystal is lifted 1-2cm above the liquid surface, and cooled to room temperature at a rate of 10-50℃ / h. Then the crystal is taken out to obtain Rb5Sb4AlSi4O 22 crystal.

[0081] The raw material rubidium carbonate in the reaction formula can be replaced by other rubidium salts such as rubidium chloride, rubidium hydroxide, rubidium oxide, rubidium bromide, rubidium nitrate, or rubidium sulfate, antimony oxide can be replaced by other antimony salts, aluminum oxide can be replaced by other aluminum salts, and silicon oxide can be replaced by other silicates.

[0082] Example 5:

[0083] Rb2CO3, Sb2O5, Al2O3, SiO2 were weighed according to the molar ratio of 5:4:1:8 into a mortar, mixed and ground, then loaded into a Φ100mmx100mm open corundum crucible, placed in a muffle furnace, slowly heated to 400℃, calcined for 24h to remove gas, then heated to 750℃, calcined for 24h, then removed and ground, then placed in a muffle furnace, and heated to 1010℃, calcined for not less than 48h to prepare the compound Rb5Sb4AlSi4O 22 powder. The powder X-ray diffraction spectrum of the obtained sample is consistent with the X-ray diffraction spectrum of the compound Rb5Sb4AlSi4O 22 .

[0084] Rb2CO3, Sb2O5, Al2O3, SiO2 were weighed according to the molar ratio of 5:4:1:8 into a mortar, mixed and ground, then loaded into a Φ100mmx100mm open corundum crucible, placed in a muffle furnace, slowly heated to 400℃, calcined for 24h to remove gas, then heated to 750℃, calcined for 24h, then removed and ground, then placed in a muffle furnace, and heated to 1010℃, calcined for not less than 48h to prepare the compound Rb5Sb4AlSi4O Figure 1 powder. The powder X-ray diffraction spectrum of the obtained sample is consistent with the X-ray diffraction spectrum of the compound Rb5Sb4AlSi4O

[0085] The prepared compound Rb5Sb4AlSi4O 22 single-phase polycrystalline powder was mixed with a fluxing agent PbO-MoO3 according to a molar ratio of 1:4, wherein the molar ratio of PbO to MoO3 was 3:2, loaded into a Φ60mmx60mm platinum-gold crucible, heated to a temperature of 1020℃, and kept at a constant temperature for not less than 48h to make the solution uniformly mixed, and then a Pt wire was lowered in, and then the temperature was lowered to induce spontaneous crystallization;

[0086] The solution was slowly cooled at a cooling rate of 1-5℃ / h to obtain a Rb5Sb4AlSi4O

[0087] seed crystal; 22 The Rb5Sb4AlSi4O

[0088] small crystal grains were used as seed crystals, and the seed crystals were fixed on a seed crystal rod by a platinum-gold wire, the seed crystals were first placed 1-2cm above the liquid surface for preheating treatment, then the seed crystals were immersed below the liquid surface at a temperature 2-10℃ higher than the saturation point, and kept at a constant temperature for 1-2h to remove impurities on the surface of the seed crystals, and then the temperature was quickly lowered to the saturation point temperature;

[0089] The solution was slowly cooled at a cooling rate of 1-5℃ / h to obtain a Rb5Sb4AlSi4O 22 crystal.

[0089] The raw material rubidium carbonate in the reaction formula can be replaced by rubidium chloride, rubidium hydroxide, rubidium oxide, rubidium bromide, rubidium nitrate or other rubidium salts, the antimony oxide can be replaced by other antimony salts, the aluminum oxide can be replaced by other aluminum salts, and the silicon oxide can be replaced by other silicates.

[0090] Example 6:

[0091] The compound Rb5Sb4AlSi4O 22 +5CO2

[0092] was synthesized according to the reaction formula: 5Rb2CO3+8SbCl3+Al2O3+8SiO2+10O2→2Rb5Sb4AlSi4O 22 .

[0093] Rb2CO3, SbCl3, Al2O3, SiO2 were weighed according to the molar ratio of 5:8:1:8, put into a mortar, mixed and ground, then loaded into a Φ100mm×100mm open corundum crucible, placed in a muffle furnace, slowly heated to 400℃, calcined for 24h to remove gas, then heated to 750℃, calcined for 24h, taken out and ground, then placed in a muffle furnace, heated to 950℃, calcined for not less than 48h to prepare the compound Rb5Sb4AlSi4O 22 single-phase polycrystalline powder. The powder X-ray diffraction spectrum of the obtained sample is consistent with the X-ray diffraction spectrum in FIG. 1 attached hereto; Figure 1

[0094] The prepared compound Rb5Sb4AlSi4O 22 single-phase polycrystalline powder was mixed with a flux K2O-MoO3 according to the molar ratio of 1:3, wherein the molar ratio of K2O to MoO3 was 3:4, loaded into a Φ60mm×60mm platinum-gold crucible, heated to a temperature of 1050℃, kept constant for not less than 48h to make the solution mixed uniformly, then a Pt wire was lowered into the solution, and then the solution was cooled to induce spontaneous crystallization;

[0095] The solution was slowly cooled at a cooling rate of 1-5℃ / h to obtain a Rb5Sb4AlSi4O 22 seed crystal;

[0096] Growth of a crystal in a compound solution: the Rb5Sb4AlSi4O 22 small crystal grain was used as a seed crystal, the seed crystal was fixed on a seed crystal rod by a platinum-gold wire, the seed crystal was first placed 1-2cm above the liquid surface for preheating treatment, then the seed crystal was immersed below the liquid surface at a temperature 2-10℃ higher than the saturation point, kept constant for 1-2h to remove impurities on the surface of the seed crystal, and then quickly cooled to the saturation point temperature;

[0097] Then the solution was cooled at a rate of 1-3℃ / day, the seed crystal rod rotated at a speed of 5-50rpm, after the growth was completed, the crystal was taken out 1-2cm above the liquid surface, cooled to room temperature at a rate of 10-50℃ / h, and then the crystal was taken out, thereby obtaining a Rb5Sb4AlSi4O 22 crystal.

[0098] The raw material rubidium carbonate in the reaction formula can be replaced by rubidium chloride, rubidium hydroxide, rubidium oxide, rubidium bromide, rubidium nitrate, rubidium sulfate or other rubidium salts, the antimony chloride can be replaced by other antimony salts, the aluminum oxide can be replaced by other aluminum salts, and the silicon oxide can be replaced by other silicates.

[0099] Example 7:

[0100] According to the reaction formula: 5Rb2CO3+4Sb2(SO4)3+Al2O3+8SiO2→2Rb5Sb4AlSi4O 22 +5CO2↑+

[0101] 4SO2↑+15O2↑Synthesis of compound Rb5Sb4AlSi4O 22 .

[0102] Rb2CO3, Sb2(SO4)3, Al2O3, SiO2 are weighed according to the molar ratio of 5:4:1:8, put into a mortar, mixed and ground, then put into a Φ100mm×100mm open corundum crucible, placed in a muffle furnace, slowly heated to 400℃, calcined for 24h to remove gas, then heated to 750℃, calcined for 24h, then taken out and ground, then put into a muffle furnace, heated to 990℃, calcined for not less than 48h to prepare compound rubidium antimony aluminum silicate single-phase polycrystalline powder. The powder X-ray diffraction spectrum of the obtained sample is consistent with the X-ray diffraction spectrum of the attached Figure 1 ;

[0103] The prepared compound lithium barium gallium silicate Rb5Sb4AlSi4O 22 single-phase polycrystalline powder is mixed with a fluxing agent PbO-MoO3-K2O according to a molar ratio of 1:3, wherein the molar ratio of K2O, MoO3 and PbO is 3:2:2, and is loaded into a platinum-gold crucible with a diameter of Φ60mm×60mm, heated to a temperature of 980℃, and kept at a constant temperature for not less than 48h to make the solution mixture uniform, and then a Pt wire is lowered into the solution, and then the solution is cooled to induce spontaneous crystallization.

[0104] The solution is slowly cooled at a cooling rate of 1-5℃ / h to obtain a rubidium antimony aluminum silicate seed crystal.

[0105] Growth of crystals in the compound solution: the Rb5Sb4AlSi4O 22 small crystal grains are used as seed crystals, and the seed crystals are fixed on the seed crystal rod by platinum-gold wire. The seed crystals are first placed 1-2cm above the liquid surface for preheating treatment, and then immersed below the liquid surface at a temperature 2-10℃ higher than the saturation point temperature, and kept at a constant temperature for 1-2h to remove impurities on the surface of the seed crystals, and then quickly cooled to the saturation point temperature.

[0106] After the temperature is decreased at a rate of 1-3 ℃ / day, the seed rod rotates at a speed of 5-50 rpm, after the growth is completed, the crystal is taken out from 1-2 cm above the liquid surface, and is decreased to room temperature at a rate of 10-50 ℃ / h, and then the crystal is taken out, so that Rb5Sb4AlSi4O 22 crystals.

[0107] The raw material rubidium carbonate in the reaction formula can be replaced by rubidium chloride, rubidium hydroxide, rubidium oxide, rubidium bromide, rubidium nitrate, rubidium sulfate or other rubidium salts, the antimony sulfate can be replaced by other antimony salts, the aluminum oxide can be replaced by other aluminum salts, and the silicon oxide can be replaced by other silicates.

Claims

1. A rubidium antimony aluminum silicate compound, characterized in that It is synthesized by high temperature solid phase reaction method, and its chemical formula is Rb5Sb4AlSi4O 22 , its molecular weight is 1405.67, and Rb5Sb4AlSi4O 22 The crystal has a non-centrosymmetric structure, belongs to the orthorhombic system, and has a space group of I4. _ m2, the unit cell parameters are Z=2.

2. The method for preparing the rubidium antimony aluminum silicate compound according to claim 1, wherein The method adopts a high-temperature solid-phase reaction method. The specific process is as follows: rubidium-containing compound, antimony-containing compound, aluminum-containing compound and silicon-containing compound raw materials are uniformly mixed, wherein the molar ratio of rubidium element in the rubidium-containing compound, antimony element in the antimony-containing compound, aluminum element in the aluminum-containing compound and silicon element in the silicon-containing compound is 4.7-5.3:3.7-4.3:0.7-1.3:3.7-4.3; the raw materials are fully ground, placed in a muffle furnace, and pre-burned at a low temperature to remove gas in the mixture; the mixture is then heated and calcined, and the mixture is taken out and ground several times during the process; and finally cooled to room temperature to obtain the compound rubidium antimony aluminum silicate Rb5Sb4AlSi4O 22 single-phase polycrystalline powder.

3. The method for preparing the rubidium antimony aluminum silicate nonlinear optical crystal according to claim 1, characterized in that: The high temperature solution method is used to prepare the product, comprising the following steps: The compound rubidium antimony aluminum silicate single-phase polycrystalline powder or any obtained compound rubidium antimony aluminum silicate single-phase polycrystalline powder and a flux are heated and heated to obtain a uniform mixed solution; Alternatively, a mixture of raw materials containing rubidium compounds, antimony compounds, aluminum compounds and silicon compounds or a mixture of raw materials containing rubidium compounds, antimony compounds, aluminum compounds and silicon compounds and flux is directly heated to obtain a uniform mixed solution; The platinum crucible containing the mixed solution is then placed in a crystal growth furnace for heating and cooling to the saturation point temperature. At this time, the seed crystal rod is inserted below the liquid surface, and then the seed crystal rod is lifted out of the liquid surface before the melt solidifies to obtain a rubidium antimony aluminum silicate nonlinear optical crystal.

4. The method for preparing the rubidium antimony aluminum silicate compound and the nonlinear optical crystal according to claims 2 and 3, characterized in that: The rubidium-containing compound includes at least one of rubidium oxide, rubidium hydroxide or a rubidium salt; the rubidium salt includes at least one of rubidium chloride, rubidium bromide, rubidium nitrate, rubidium carbonate and rubidium sulfate; The antimony-containing compound is at least one of antimony oxide, antimony hydroxide or antimony salt; the antimony salt includes at least one of antimony chloride and antimony sulfate; The aluminum-containing compound is at least one of aluminum oxide or aluminum salt; the aluminum salt includes at least one of aluminum chloride, aluminum bromide, aluminum nitrate, and aluminum sulfate; The silicon-containing compound is at least one of silicon oxide or silicon salt; the silicon salt includes at least one of silicon chloride and silicon bromide.

5. The method for preparing the rubidium antimony aluminum silicate nonlinear optical crystal according to claim 3, wherein: The high-temperature solution method is used to grow rubidium antimony aluminum silicate nonlinear optical crystals, and the molar ratio of the compound rubidium antimony aluminum silicate single-phase polycrystalline powder to the flux is 1:0-20; or the molar ratio of the rubidium compound, the antimony compound, the aluminum compound, the silicon compound and the flux is 4.7-5.3:3.7-4.3:0.7-1.3:3.7-4.3:0-20.

6. The method for preparing the rubidium antimony aluminum silicate nonlinear optical crystal according to claim 3, wherein: The flux includes boric acid, potassium oxide, lead oxide, potassium salt, lead fluoride, molybdenum oxide, bismuth oxide, potassium fluoride or a composite flux, wherein the composite flux includes one of K2O-PbO, KF-PbF2, KF-MoO3, K2O-MoO3, K2O-Bi2O3, PbO-MoO3 or PbO-MoO3-K2O.

7. The method for preparing the rubidium antimony aluminum silicate nonlinear optical crystal according to claim 3 or 6, characterized in that: The molar ratio of K2O:PbO in the composite flux K2O-PbO system is 1-4:2-7; the molar ratio of KF:PbF2 in the KF-PbF2 system is 1-9:1-5; the molar ratio of KF:MoO3 in the KF-MoO3 system is 2-8:1-5; the molar ratio of K2O:MoO3 in the K2O-MoO3 system is 1-3:2-5; the molar ratio of K2O:Bi2O3 in the K2O-Bi2O3 system is 1-7:1-5; the molar ratio of PbO:MoO3 in the PbO-MoO3 system is 1-3:2-6; and the molar ratio of PbO:MoO3:K2O in the PbO-MoO3-K2O system is 1-3:2-4:2-8.

8. The use of the rubidium antimony aluminum silicate nonlinear optical crystal according to claim 1, characterized in that: Rubidium antimony aluminum silicate nonlinear optical crystals can be used to make frequency doubling generators, frequency converters and optical parametric oscillators.

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