阅读说明：本技术 化合物锗酸锌铷非线性光学晶体及其制备方法和用途 (Compound zinc-rubidium germanate nonlinear optical crystal and preparation method and application thereof ) 是由 胡章贵 韩涛 李从刚 于 2021-09-06 设计创作，主要内容包括：本发明公开了一种化合物锗酸锌铷非线性光学晶体及其制备方法和用途,该化合物的化学式为Rb-(2)ZnGe-(2)O-(6),其制备方法是,将含铷化合物、含锌化合物、含锗化合物原料均匀混合并充分研磨,置于马弗炉中,先低温下预烧除去原料中的水分和气体,再升温锻烧,期间多次取出研磨并继续锻烧,制得化合物锗酸锌铷。进一步的将化合物与助熔剂混合升温得到混合溶液,在晶体生长炉中,制备出锗酸锌铷非线性光学晶体。本发明的技术效果是：所获晶体具有优良的热稳定性,较宽的透光范围,硬度适中,物化性能稳定等优点,采用本发明所述方法获得的化合物锗酸锌铷可用于制备倍频器件。(The invention discloses a compound rubidium zinc germanate nonlinear optical crystal, a preparation method and application thereof, wherein the chemical formula of the compound is Rb 2 ZnGe 2 O 6 The preparation method comprises the steps of uniformly mixing and fully grinding raw materials of rubidium-containing compound, zinc-containing compound and germanium-containing compound, placing the mixture in a muffle furnace, pre-burning at low temperature to remove moisture and gas in the raw materials, heating and calcining, taking out the mixture for a plurality of times during the calcining, and continuing to calcine to obtain the compound of zinc germanate and rubidium. Further mixing the compound with fluxing agent, heating to obtain mixed solution, and placing in crystal growth furnaceAnd preparing the zinc rubidium germanate nonlinear optical crystal. The invention has the technical effects that: the obtained crystal has the advantages of excellent thermal stability, wider light transmission range, moderate hardness, stable physical and chemical properties and the like, and the compound rubidium zinc germanate obtained by the method can be used for preparing frequency doubling devices.)

1. The compound rubidium zinc germanate nonlinear optical crystal is characterized in that the chemical formula of the compound is Rb₂ZnGe₂O₆Molecular weight 238.74, not containing a center of symmetry, belonging to the orthorhombic system, space group C222₁Cell parameter ofThe ultraviolet cut-off edge of the compound is 315 nm.

2. The method for preparing the compound rubidium zinc germanate nonlinear optical crystal according to claim 1, wherein the rubidium zinc germanate nonlinear optical crystal is prepared by a molten salt growth method, and the method comprises the following steps:

a. mixing rubidium-containing compound, zinc-containing compound and germanium-containing compound to prepare zinc germanate, rubidium germanate and Rb through a solid-phase reaction method₂ZnGe₂O₆Wherein the molar ratio of the element rubidium in the rubidium-containing compound to the element zinc in the zinc-containing compound to the element germanium in the germanium-containing compound is 2:1: 2;

b. the compound zinc-rubidium germanate is prepared by a solid-phase reaction method, and the specific process comprises the following steps: fully and uniformly mixing rubidium-containing compound, zinc-containing compound and germanium-containing compound raw materials, grinding, placing in a muffle furnace, calcining at low temperature to remove moisture and gas in the mixed materials, heating and continuing calcining, taking out and grinding for multiple times during the calcining, and cooling to room temperature to obtain a compound zinc germanate rubidium;

the rubidium-containing compound comprises at least one of rubidium oxide, rubidium hydroxide, or a rubidium salt; the rubidium salt comprises at least one of rubidium chloride, rubidium bromide, rubidium nitrate, rubidium carbonate, rubidium bicarbonate and rubidium sulfate;

the zinc-containing compound is at least one of zinc oxide or zinc salt; the zinc salt comprises at least one of zinc chloride, zinc nitrate, zinc bicarbonate and zinc sulfate;

the germanium-containing compound is at least one of germanium oxide or germanium salt; the germanium salt comprises at least one of germanium chloride, germanium bromide, germanium nitrate, germanium carbonate, germanium bicarbonate, and germanium sulfate;

heating any one of the obtained compound zinc-rubidium germanate single-phase polycrystalline powder or a mixture of any one of the obtained compound zinc-rubidium germanate single-phase polycrystalline powder and a fluxing agent to obtain a uniform mixed melt;

or directly heating and melting a mixture of the rubidium-containing compound, the zinc-containing compound and the germanium-containing compound or a mixture of the rubidium-containing compound, the zinc-containing compound, the germanium-containing compound and a fluxing agent to obtain uniform mixed melt;

c. and c, placing the Pt crucible containing the mixed solution prepared in the step b into a crystal growth furnace, fixing one end of the seed crystal by using a platinum wire, putting the other end of the seed crystal into the liquid surface to melt off surface impurities or defects when the temperature is 5-10 ℃ higher than the saturation point, and then quickly cooling to below the saturation temperature or growing at constant temperature to prepare the rubidium zinc germanate nonlinear optical crystal.

3. The method for preparing the rubidium zinc germanate nonlinear optical crystal according to claim 2, wherein the molar ratio of the compound rubidium zinc germanate single-phase polycrystalline powder to the fluxing agent is 1: 0-20; the flux comprises rubidium hydroxide, germanium hydroxide, rubidium oxide, germanium oxide, rubidium salt, germanium salt, lead oxide or composite flux, wherein the composite flux comprises Rb₂O-GeO₂、RbF-GeO₂、RbF-TeO₂,、Rb₂O-TeO₂,、GeO₂-TeO₂Or GeO₂-TeO₂-Rb₂And O is one of the compounds.

4. The method for preparing the rubidium zinc germanate nonlinear optical crystal according to claim 3, wherein a composite fluxing agent Rb is used₂O-GeO₂In the system of Rb₂O and GeO₂The molar ratio of (A) to (B) is 1-4: 2-6; RbF-GeO₂RbF and GeO in the system₂The molar ratio of (A) to (B) is 1-6: 2-4; rb₂O-TeO₂In the system of Rb₂O and TeO₂Is prepared from (A) and (B)The molar ratio is 1-3: 2-6; RbF-TeO₂RbF and TeO in the system₂The molar ratio of (1-8) to (2-4); GeO₂-TeO₂GeO in the system₂And TeO₂The molar ratio of (A) to (B) is 1-3: 2-6; GeO₂-TeO₂-Rb₂GeO in O system₂And TeO₂And Rb₂The molar ratio of O is 1-3:2-4: 2-6.

5. Use of the rubidium zinc germanate nonlinear optical crystal of claim 1, wherein the rubidium zinc germanate nonlinear optical crystal is used for manufacturing a frequency doubling generator, an upper frequency converter, a lower frequency converter and an optical parametric oscillator.

Technical Field

The invention relates to compounds of the formula Rb₂ZnGe₂O₆Compound (2) zinc rubidium germanate anda zinc-rubidium germanate nonlinear optical crystal, a preparation method of the crystal and a nonlinear optical device manufactured by using the crystal.

Background

The nonlinear optical crystal (NLO) can realize the conversion of laser wavelength, and is a key material for preparing optical devices, because of good stability and high laser damage threshold, inorganic nonlinear optical crystal has gained important application in military affairs, medical treatment, precision processing and communication field₂O₄) Crystal, LBO (LiB)₃O₅) Crystal, KBe₂BO₃F₂(KBBF) crystal, KDP (KH)₂PO₄) Crystal, LN (LiNbO)₃) Crystals, and the like. Although these materials have great application value, some defects exist, such as phase change problem of BBO crystal in the growth process, deliquescence problem of CLBO and KDP crystal, lamellar growth habit and extremely toxic raw material problem of KBBF crystal, low laser damage threshold of LN crystal and the like. With the continuous progress and development of science and technology, high and new technologies put forward higher requirements on nonlinear optical crystals, and the development of novel inorganic nonlinear optical crystal materials with excellent performance is particularly urgent.

The germanate crystal has excellent properties such as good stability, wide light-transmitting wave band, high damage threshold and the like, and is an excellent candidate material for a nonlinear optical crystal material. Will d¹⁰Zn of electronic structure²⁺Cation and electron transition alkali metal cation (Rb) having no d-d in ultraviolet region⁺) With GeO₄The combination of groups aims to increase the transmission range and the frequency doubling response of the germanate. Therefore, the design and synthesis of the alkali metal zinc-containing germanate nonlinear optical crystal with excellent comprehensive performance are of great significance.

Disclosure of Invention

The invention aims to provide a compound rubidium zinc germanate nonlinear optical crystal with a chemical formula of Rb₂ZnGe₂O₆；

The second purpose of the invention is to provide a preparation method for synthesizing a compound rubidium zinc germanate by adopting a solid phase reaction method and growing a rubidium zinc germanate nonlinear optical crystal by adopting a high-temperature melt method;

the third purpose of the invention is to provide the application of the rubidium zinc germanate nonlinear optical device.

The technical scheme for realizing the purpose is as follows:

the chemical formula of the compound zinc-rubidium germanate provided by the invention is Rb₂ZnGe₂O₆(ii) a Uniformly mixing and fully grinding raw materials of a rubidium-containing compound, a zinc-containing compound and a germanium-containing compound, placing the raw materials in a muffle furnace, pre-burning at low temperature to remove moisture and gas in the raw materials, heating and calcining, taking out and grinding for multiple times during the heating and calcining, and continuously calcining to obtain a compound, namely, zinc-rubidium germanate;

the rubidium-containing compound comprises at least one of rubidium oxide, rubidium carbonate, rubidium bicarbonate, rubidium sulfate, rubidium hydroxide or rubidium salt;

the zinc-containing compound is at least one of zinc oxide or zinc salt; the zinc salt comprises at least one of zinc chloride, zinc nitrate, zinc oxalate and zinc sulfate;

the germanium-containing compound is at least one of germanium oxide or germanium salt; the germanium salt comprises at least one of germanium chloride, germanium bromide, germanium nitrate, germanium oxalate, germanium carbonate, germanium bicarbonate, and germanium sulfate.

The zinc-rubidium germanate compound can be prepared according to the following chemical reaction formula by adopting a solid-phase reaction method:

1)Rb₂CO₃+ZnO+2GeO₂→Rb₂ZnGe₂O₆+CO₂↑

2)2RbHCO₃+ZnO+2GeO₂→Rb₂ZnGe₂O₆+H₂O↑+2CO₂↑

3)2RbNO₃+ZnO+2GeO₂→Rb₂ZnGe₂O₆+2NO₂↑+0.5O₂↑

4)2Rb(OH)+ZnO+2GeO₂→Rb₂ZnGe₂O₆+H₂O↑+

5)2Rb₂(SO₄)+2ZnO+4GeO₂→2Rb₂ZnGe₂O₆+2SO₂↑+O₂↑

6)Rb₂O+ZnO+2GeCl₄+2O₂→Rb₂ZnGe₂O₆+4Cl₂↑

7)2RbF+ZnO+2GeO₂+0.5O₂→Rb₂ZnGe₂O₆+F₂↑

8)2RbCl+ZnO+2GeO₂+0.5O₂→Rb₂ZnGe₂O₆+Cl₂↑

9)2RbBr+ZnO+2GeO₂+0.5O₂→Rb₂ZnGe₂O₆+Br₂↑

10)Rb₂O+ZnO+2GeO₂→Rb₂ZnGe₂O₆

11)2Rb₂(C₂O₄)+2ZnO+4GeO₂→2Rb₂ZnGe₂O₆+4CO↑+O₂↑

12)Rb₂CO₃+Zn(NO₃)₂+2GeO₂→Rb₂ZnGe₂O₆+CO₂↑+2NO₂↑+0.5O₂↑

13)Rb₂O+Zn(NO₃)₂+2GeO₂→Rb₂ZnGe₂O₆+2NO₂↑+0.5O₂↑

14)2RbNO₃+Zn(NO₃)₂+2GeO₂→Rb₂ZnGe₂O₆+4NO₂↑+O₂↑

15)2Rb(OH)+Zn(NO₃)₂+2GeO₂→Rb₂ZnGe₂O₆+2NO₂↑+H₂O↑+O₂↑

16)2RbHCO₃+Zn(NO₃)₂+2GeO₂→Rb₂ZnGe₂O₆+H₂O↑+2CO₂↑+2NO₂↑+0.5O₂↑

17)Rb₂CO₃+Zn(Cl)₂+0.5O₂+2GeO₂→Rb₂ZnGe₂O₆+CO₂↑+Cl₂↑

18)Rb₂CO₃+ZnSO₄+2GeO₂→Rb₂ZnGe₂O₆+CO₂↑+SO₂↑+0.5O₂↑

the invention provides a zinc-rubidium germanate nonlinear optical crystal, the chemical formula of the compound is Rb₂ZnGe₂O₆Molecular weight 238.74, not containing a center of symmetry, belonging to the orthorhombic system, space group C222₁Cell parameter of The ultraviolet cut-off edge is 315nm, and the product has stable property and is not deliquescent.

The invention provides a preparation method of rubidium zinc germanate nonlinear optical crystal, which adopts a molten salt growth method to grow the rubidium zinc germanate nonlinear optical crystal, and the specific growth scheme is as follows:

a. uniformly mixing the compound zinc-rubidium germanate single-phase polycrystalline powder with a fluxing agent, heating the mixture to the temperature of 850-;

or directly heating a mixture of the rubidium-containing compound, the zinc-containing compound and the germanium-containing compound or a mixture of the rubidium-containing compound, the zinc-containing compound, the germanium-containing compound and a fluxing agent to 1150 ℃ at a temperature rise rate of 1-100 ℃/h, keeping the temperature for not less than 24 hours to obtain a mixed melt, and then cooling to 1000 ℃ at a temperature of 600 ℃, wherein the molar ratio of the rubidium-containing compound, the zinc-containing compound and the germanium-containing compound to the fluxing agent is 1:1:2: 0-20;

the fluxing agent is primarily a self fluxing agent, such as Rb₂CO₃、Rb₂O、RbOH、RbF、RbCl、GeO₂Rubidium salt, germanium salt or composite adjuvantFluxes, e.g. Rb₂CO₃-GeO₂、Rb₂O-GeO₂、RbF-GeO₂、RbCl-GeO₂、Rb₂CO₃-TeO₂、Rb₂O-TeO₂、RbF-TeO₂、RbCl-TeO₂、GeO₂-TeO₂、GeO₂-TeO₂-Rb₂O、GeO₂-TeO₂-Rb₂CO₃One or more of (a).

The compound zinc-rubidium germanate single-phase polycrystalline powder is prepared by adopting a solid-phase synthesis method, and comprises the following steps of mixing a rubidium-containing compound, a zinc-containing compound and a germanium-containing compound, preparing zinc-rubidium germanate by adopting a solid-phase reaction method, uniformly mixing raw materials of the rubidium-containing compound, the zinc-containing compound and the germanium-containing compound, grinding, placing the mixture into a Pt crucible and placing the Pt crucible into a muffle furnace, pre-burning to remove moisture and gas in the raw materials, heating to the temperature of 500-850 ℃, taking out the mixture for grinding for many times and continuing to calcine, wherein the calcining time is not less than 72 hours, and cooling to the room temperature to obtain the compound zinc-rubidium germanate single-phase polycrystalline powder.

b. B, preparing zinc germanate rubidium seed crystals, namely slowly cooling the mixed melt obtained in the step a to room temperature at the speed of 0.5-10 ℃/h, and spontaneously crystallizing to obtain the zinc germanate rubidium seed crystals;

c. placing the Pt crucible containing the mixed melt prepared in the step a into a crystal growth furnace, fixing the seed crystal obtained in the step b on a seed crystal rod, putting the seed crystal above the liquid level from top to bottom, preheating the seed crystal for 10-30 minutes, putting the seed crystal on the liquid level of the melt when the temperature is 5-10 ℃ higher than the saturation point, keeping the temperature for 5-10 minutes to remove impurities on the surface of the seed crystal, and then reducing the temperature to the saturation point at the cooling rate of 1-10 ℃/min;

d. and slowly cooling at the speed of 1-5 ℃/day, growing at the rotating speed of 5-50rpm of the seed rod, after the crystal grows to the required size, lifting the crystal to be 1cm above the liquid level, cooling to the room temperature at the speed of 10-100 ℃/h, and finally opening a hearth to take out the crystal to obtain the rubidium zinc germanate nonlinear optical crystal.

The fluxing agent Rb₂CO₃-GeO₂In the system of Rb₂CO₃With GeO₂The molar ratio of (A) to (B) is 1-4: 2-6; rb₂O-GeO₂In the system of Rb₂O and GeO₂The molar ratio of (A) to (B) is 1-4: 2-6; RbF-GeO₂RbF and GeO in the system₂The molar ratio of (A) to (B) is 1-6: 2-4; RbCl-GeO₂RbCl and GeO in the system₂The molar ratio of (A) to (B) is 1-6: 2-4; rb₂CO₃-TeO₂In the system of Rb₂CO₃And TeO₂The molar ratio of (A) to (B) is 1-3: 2-6; rb₂O-TeO₂In the system of Rb₂O and TeO₂The molar ratio of (A) to (B) is 1-3: 2-6; RbF-TeO₂RbF and TeO in the system₂The molar ratio of (1-8) to (2-4); RbCl-TeO₂RbCl and TeO in the system₂The molar ratio of (1-8) to (2-4); GeO₂-TeO₂GeO in the system₂And TeO₂The molar ratio of (A) to (B) is 1-3: 2-6; GeO₂-TeO₂-Rb₂CO₃GeO in the system₂And TeO₂And Rb₂CO₃The molar ratio of (1-3: 2-4: 2-6); GeO₂-TeO₂-Rb₂GeO in O system₂And TeO₂And Rb₂The molar ratio of O is 1-3:2-4: 2-6;

the chemical formula of the zinc rubidium germanate nonlinear optical crystal prepared by the invention is Rb₂ZnGe₂O₆Molecular weight 238.74, not containing a center of symmetry, belonging to the orthorhombic system, space group C222₁Cell parameter of The ultraviolet cut-off edge is 315nm, and the thermal stability is excellent.

Because Rb is used in the process of growing the rubidium zinc germanate nonlinear optical crystal₂CO₃、Rb₂O、RbOH、RbF、RbCl、GeO₂Rubidium or germanium salts, self-fluxing agents or composite fluxing agents, e.g. Rb₂CO₃-GeO₂、Rb₂O-GeO₂、RbF-GeO₂、RbCl-GeO₂、Rb₂CO₃-TeO₂、Rb₂O-TeO₂、RbF-TeO₂、RbCl-TeO₂、GeO₂-TeO₂，GeO₂-TeO₂-Rb₂O、GeO₂-TeO₂-Rb₂CO₃And the like, target crystals with larger sizes are easily obtained; the obtained crystal has the advantages of excellent thermal stability, wider light transmission range, moderate hardness, stable physical and chemical properties and the like. The compound rubidium zinc germanate obtained by the method can be used for preparing a frequency doubling device, and at room temperature, a Nd-YAG Q-switched laser light source is adopted, infrared light with the incident wavelength of 1064nm is incident, and green laser with the wavelength of 532nm can be output.

Drawings

FIG. 1 is Rb of the present invention₂ZnGe₂O₆The X-ray diffraction pattern of the powder is similar to the X-ray diffraction pattern based on the simulation of the crystal structure.

FIG. 2 shows Rb of the present invention₂ZnGe₂O₆The structure diagram of the unit cell.

FIG. 3 shows Rb according to the present invention₂ZnGe₂O₆Ultraviolet and visible diffuse reflectance spectrum.

FIG. 4 shows Rb of the present invention₂ZnGe₂O₆The working principle of the nonlinear optical device made of crystal is shown schematically, wherein 1 is a laser, 2 is an incident laser beam, and 3 is Rb₂ZnGe₂O₆Crystal, 4 the laser beam generated and 5 a filter.

Detailed Description

The invention is described in detail below with reference to the following figures and examples:

example 1:

according to the reaction formula: rb₂CO₃+ZnO+2GeO₂→Rb₂ZnGe₂O₆+CO₂↓ [ O ] synthetic compound Rb₂ZnGe₂O₆；

Will Rb₂CO₃ZnO and GeO₂Weighing according to the molar ratio of 1:1:2, putting into a mortar, uniformly mixing and grinding, and then putting into an opening with the diameter of 60mm multiplied by 60mmPlacing the corundum crucible in a muffle furnace, slowly heating to 350 ℃ for calcination, keeping the temperature for 24 hours to remove moisture and gas, heating to 750 ℃ for calcination for 24 hours, taking out the corundum crucible, grinding, placing the corundum crucible in the muffle furnace, heating to 800 ℃ for calcination for not less than 48 hours to prepare compound zinc rubidium germanate single-phase polycrystalline powder, and analyzing by using powder X-ray diffraction test, wherein the X-ray spectrogram of the obtained sample powder and zinc rubidium Rb germanate₂ZnGe₂O₆The theoretical X-ray spectrograms obtained from the single crystal structure are consistent, and refer to the attached figure 1;

the prepared compound of zinc germanate, rubidium and Rb₂ZnGe₂O₆Single-phase polycrystalline powder and fluxing agent RbF-GeO₂With a molar ratio Rb₂ZnGe₂O₆:RbF-GeO₂1:3, wherein RbF and GeO₂The molar ratio of the Pt filaments to the Pt filaments is 4:1, uniformly mixing, pressing, putting into a Pt crucible with the diameter of 60mm multiplied by 60mm, heating the mixed raw materials to 850 ℃ at the heating rate of 10-100 ℃/h, keeping the temperature for not less than 24 hours to uniformly mix the melt, putting the Pt filaments into the liquid level, and then cooling to induce spontaneous crystallization; the crystal has the chemical formula of Rb₂ZnGe₂O₆Molecular weight 238.74, not containing a center of symmetry, belonging to the orthorhombic system, space group C222₁Cell parameter of The ultraviolet cut-off edge is 315nm, and the product has stable property and is not deliquescent, see figure 2 and figure 3.

Slowly cooling the melt at the speed of 1-5 ℃/h to obtain zinc germanate rubidium seed crystals;

growing crystals in a compound melt: subjecting Rb obtained by spontaneous crystallization to₂ZnGe₂O₆Fixing seed crystal on seed crystal rod by platinum wire, preheating seed crystal 1-2cm above liquid surface, immersing seed crystal below liquid surface at 5-10 deg.C above saturation point, maintaining for 5-10 min to remove surface impurities, and rapidly cooling to saturation point；

Cooling at a rate of 1-3 deg.C/day with seed rod rotation speed of 5-50rpm, cooling to room temperature at a rate of 10-50 deg.C/hr for crystal extraction liquid level 1cm above, and taking out crystal to obtain Rb₂ZnGe₂O₆And (4) crystals.

The rubidium carbonate used as the raw material in the reaction formula may be replaced by other rubidium-containing salts such as rubidium oxide, rubidium chloride, rubidium bromide, rubidium nitrate, rubidium oxalate, rubidium hydroxide, rubidium bicarbonate or rubidium sulfate, etc., the zinc oxide may be replaced by other zinc-containing salts such as zinc chloride, zinc nitrate, zinc oxalate or zinc sulfate, etc., and the germanium oxide may be replaced by other germanium salts.

Example 2:

according to the reaction formula: 2RbNO₃+ZnO+2GeO₂→Rb₂ZnGe₂O₆+2NO₂↑+0.5O₂↓ [ O ] synthetic compound Rb₂ZnGe₂O₆；

Converting RbNO₃ZnO and GeO₂Directly weighing raw materials according to the mol ratio of 2:1:2, and mixing the weighed raw materials with a fluxing agent Rb₂O-GeO₂Mixing according to a molar ratio of 1:3, wherein Rb is₂O and GeO₂The molar ratio of the Pt filament to the Pt filament is 4:1, the mixture is put into a platinum crucible with the diameter of 60mm multiplied by 60mm, the temperature is raised to 950 ℃, the constant temperature is kept for not less than 24 hours, the melt is uniformly mixed, the Pt filament is added, and then the temperature is reduced to induce spontaneous crystallization;

slowly cooling at the cooling rate of 1-5 ℃/h, and spontaneously crystallizing to obtain zinc germanate rubidium seed crystals;

growing crystals in a compound melt: subjecting Rb obtained by spontaneous crystallization to₂ZnGe₂O₆Using small crystal grains as seed crystals, fixing the seed crystals on a seed crystal rod by using a platinum wire, firstly placing the seed crystals above the liquid level for preheating treatment at a position of 1-2cm, then immersing the seed crystals below the liquid level when the temperature is 5-10 ℃ higher than the saturation point, keeping for 5-10 minutes to remove surface impurities, and then quickly cooling to the saturation point temperature;

cooling at a rate of 1-3 deg.C/day with seed rod rotation speed of 5-50rpm, removing liquid surface of the crystal after crystal growth, and cooling to room temperature at a rate of 10-50 deg.C/hTaking out the crystal from the furnace to obtain Rb₂ZnGe₂O₆And (4) crystals.

The rubidium nitrate used as the raw material in the reaction formula may be replaced by other rubidium-containing salts such as rubidium oxide, rubidium chloride, rubidium bromide, rubidium carbonate, rubidium oxalate, rubidium hydroxide, rubidium bicarbonate or rubidium sulfate, etc., the zinc oxide may be replaced by other zinc-containing salts such as zinc chloride, zinc nitrate, zinc oxalate or zinc sulfate, etc., and the germanium oxide may be replaced by other germanium salts.

Example 3:

according to the reaction formula: 2Rb (OH) + ZnO +2GeO₂→Rb₂ZnGe₂O₆+H₂O ↓syntheticcompound Rb₂ZnGe₂O₆；

Rb (OH), ZnO and GeO₂Directly weighing raw materials according to the mol ratio of 2:1:2, and mixing the weighed raw materials with a fluxing agent RbF-TeO₂Mixing according to the mol ratio of 1:3, wherein RbF and TeO₂The molar ratio of the Pt filament to the Pt filament is 3:1, the mixture is put into a platinum crucible with the diameter of 60mm multiplied by 60mm, the temperature is raised to 900 ℃, the constant temperature is kept for not less than 24 hours, the melt is uniformly mixed, the Pt filament is added, and then the temperature is reduced to induce spontaneous crystallization;

slowly cooling the melt at the speed of 1-5 ℃/h to obtain zinc germanate rubidium seed crystals;

growing crystals in a compound melt: subjecting Rb obtained by spontaneous crystallization to₂ZnGe₂O₆Using small crystal grains as seed crystals, fixing the seed crystals on a seed crystal rod by using a platinum wire, firstly placing the seed crystals above the liquid level for preheating treatment at a position of 1-2cm, then immersing the seed crystals below the liquid level when the temperature is 5-10 ℃ higher than the saturation point, keeping for 5-10 minutes to remove surface impurities, and then quickly cooling to the saturation point temperature;

cooling at a rate of 1-3 deg.C/day, rotating the seed rod at 5-50rpm, removing the crystal liquid surface after crystal growth, cooling to room temperature at a rate of 10-50 deg.C/hr, and taking out the crystal from the furnace to obtain Rb₂ZnGe₂O₆And (4) crystals.

The rubidium hydroxide as the raw material in the reaction formula may be replaced by other rubidium-containing salts such as rubidium oxide, rubidium chloride, rubidium bromide, rubidium carbonate, rubidium nitrate, rubidium oxalate, rubidium bicarbonate, and rubidium sulfate, the zinc oxide may be replaced by other zinc-containing salts such as zinc chloride, zinc nitrate, zinc oxalate, and zinc sulfate, and the germanium oxide may be replaced by other germanium salts.

Example 4:

according to the reaction formula: 2Rb₂SO₄+2ZnO+4GeO₂→2Rb₂ZnGe₂O₆+2SO₂↑+O₂↓ [ O ] synthetic compound Rb₂ZnGe₂O₆；

Will Rb₂(SO₄)，ZnO，GeO₂Directly weighing raw materials according to the mol ratio of 1:1:2, and mixing the weighed raw materials with a fluxing agent GeO₂-TeO₂Mixing according to a molar ratio of 1:3, wherein GeO is₂And TeO₂The molar ratio of the Pt filament to the Pt filament is 1:4, the mixture is put into a platinum crucible with the diameter of 60mm multiplied by 60mm, the temperature is raised to 900 ℃, the constant temperature is kept for not less than 24 hours, the melt is uniformly mixed, the Pt filament is added, and then the temperature is reduced to induce spontaneous crystallization;

slowly cooling the melt at the speed of 1-5 ℃/h to obtain zinc germanate rubidium seed crystals;

growing crystals in a compound melt: subjecting Rb obtained by spontaneous crystallization to₂ZnGe₂O₆Using small crystal grains as seed crystals, fixing the seed crystals on a seed crystal rod by using a platinum wire, firstly placing the seed crystals above the liquid level for preheating treatment at a position of 1-2cm, then immersing the seed crystals below the liquid level at a temperature of 5 ℃ higher than the saturation point, keeping for 10 minutes to remove surface impurities, and then rapidly cooling to the saturation temperature of 850 ℃;

cooling at a rate of 1-3 deg.C/day, rotating the seed rod at 5-50rpm, removing the crystal liquid surface after crystal growth, cooling to room temperature at a rate of 10-50 deg.C/hr, and taking out the crystal from the furnace to obtain Rb₂ZnGe₂O₆And (4) crystals.

The raw material rubidium sulfate in the reaction formula can be replaced by other rubidium-containing salts such as rubidium oxide, rubidium chloride, rubidium bromide, rubidium carbonate, rubidium nitrate, rubidium oxalate, rubidium bicarbonate or rubidium hydroxide, etc., zinc oxide can be replaced by other zinc-containing salts such as zinc chloride, zinc nitrate, zinc oxalate or zinc sulfate, etc., and germanium oxide can be replaced by other germanium salts.

Example 5:

according to the reaction formula: 2RbCl + ZnO +2GeO₂+0.5O₂→Rb₂ZnGe₂O₆+Cl₂↓ [ O ] synthetic compound Rb₂ZnGe₂O₆；

Mixing RbCl, ZnO and GeO₂Directly weighing raw materials according to the mol ratio of 2:1:2, and mixing the weighed raw materials with a fluxing agent RbF-TeO₂Uniformly mixing according to the molar ratio of 1:2, wherein RbF and TeO are₂The molar ratio of the Pt filament to the Pt filament is 3:1, the mixture is put into a platinum crucible with the diameter of 60mm multiplied by 60mm, the temperature is raised to 850 ℃, the constant temperature is kept for not less than 24 hours, the melt is uniformly mixed, and the Pt filament is put into the crucible at the same time, and then the temperature is reduced to induce spontaneous crystallization;

slowly cooling the melt at the speed of 1-5 ℃/h to obtain zinc germanate rubidium seed crystals;

growing crystals in a compound melt: subjecting Rb obtained by spontaneous crystallization to₂ZnGe₂O₆Using small crystal grains as seed crystals, fixing the seed crystals on a seed crystal rod by using a platinum wire, firstly placing the seed crystals above the liquid level for preheating treatment at a position of 1-2cm, then immersing the seed crystals below the liquid level when the temperature is 5-10 ℃ higher than the saturation point, keeping for 5-10 minutes to remove surface impurities, and then quickly cooling to the saturation point temperature;

cooling at a rate of 1-3 deg.C/day, rotating the seed rod at 5-50rpm, removing the crystal liquid surface after crystal growth, cooling to room temperature at a rate of 10-50 deg.C/hr, and taking out the crystal from the furnace to obtain Rb₂ZnGe₂O₆And (4) crystals.

The rubidium chloride used as raw material in the reaction formula may be replaced by other rubidium-containing salts such as rubidium oxide, rubidium bromide, rubidium carbonate, rubidium nitrate, rubidium oxalate, rubidium bicarbonate, rubidium hydroxide, and rubidium sulfate, the zinc oxide may be replaced by other zinc-containing salts such as zinc chloride, zinc nitrate, zinc oxalate, and zinc sulfate, and the germanium oxide may be replaced by other germanium salts.

Example 6:

according to the reaction formula: 2RbBr + ZnO +2GeO₂+0.5O₂→Rb₂ZnGe₂O₆+Br₂↓ [ O ] synthetic compound Rb₂ZnGe₂O₆；

Mixing RbBr, ZnO and GeO₂Directly weighing raw materials according to the mol ratio of 2:1:2, and mixing the weighed raw materials with a fluxing agent RbF-TeO₂Uniformly mixing according to the molar ratio of 1:2, wherein RbF and TeO are₂The molar ratio of the Pt filament to the Pt filament is 3:1, the mixture is put into a platinum crucible with the diameter of 60mm multiplied by 60mm, the temperature is raised to 850 ℃, the constant temperature is kept for not less than 24 hours, the melt is uniformly mixed, the Pt filament is added, and then the temperature is reduced to induce spontaneous crystallization;

slowly cooling the melt at the speed of 1-5 ℃/h to obtain zinc germanate rubidium seed crystals;

growing crystals in a compound melt: subjecting Rb obtained by spontaneous crystallization to₂ZnGe₂O₆Using small crystal grains as seed crystals, fixing the seed crystals on a seed crystal rod by using a platinum wire, firstly placing the seed crystals above the liquid level for preheating treatment at a position of 1-2cm, then immersing the seed crystals below the liquid level when the temperature is 5-10 ℃ higher than the saturation point, keeping for 5-10 minutes to remove surface impurities, and then quickly cooling to the saturation point temperature;

cooling at a rate of 1-3 deg.C/day, rotating the seed rod at 5-50rpm, removing the crystal liquid surface after crystal growth, cooling to room temperature at a rate of 10-50 deg.C/hr, and taking out the crystal from the furnace to obtain Rb₂ZnGe₂O₆And (4) crystals.

The rubidium bromide used as the raw material in the reaction formula may be replaced by other rubidium-containing salts such as rubidium oxide, rubidium chloride, rubidium carbonate, rubidium nitrate, rubidium oxalate, rubidium bicarbonate, rubidium hydroxide, and rubidium sulfate, the zinc oxide may be replaced by other zinc-containing salts such as zinc chloride, zinc nitrate, zinc oxalate, and zinc sulfate, and the germanium oxide may be replaced by other germanium salts.

Example 7:

according to the reaction formula: rb₂O+ZnO+2GeO₂→Rb₂ZnGe₂O₆Synthesis of Compound Rb₂ZnGe₂O₆；

Will Rb₂O, ZnO and GeO₂Directly weighing raw materials according to the mol ratio of 1:1:2, and mixing the weighed raw materials with a fluxing agent GeO₂-TeO₂-Rb₂Mixing O at a molar ratio of 1:1, wherein GeO₂And TeO₂And Rb₂The molar ratio of O is 1:2:2, the mixture is put into a platinum crucible with the diameter of 60mm multiplied by 60mm, the temperature is raised to 950 ℃, the melt is uniformly mixed, meanwhile, Pt filaments are put in, and then the temperature is reduced to induce spontaneous crystallization;

slowly cooling the melt at the speed of 1-5 ℃/h to obtain zinc germanate rubidium seed crystals;

growing crystals in a compound melt: subjecting Rb obtained by spontaneous crystallization to₂ZnGe₂O₆Using small crystal grains as seed crystals, fixing the seed crystals on a seed crystal rod by using a platinum wire, firstly placing the seed crystals above the liquid level for preheating treatment at a position of 1-2cm, then immersing the seed crystals below the liquid level when the temperature is 5-10 ℃ higher than the saturation point, keeping for 5-10 minutes to remove surface impurities, and then quickly cooling to the saturation point temperature;

cooling at a rate of 1-3 deg.C/day, rotating the seed rod at 5-50rpm, removing the crystal liquid surface after crystal growth, cooling to room temperature at a rate of 10-50 deg.C/hr, and taking out the crystal from the furnace to obtain Rb₂ZnGe₂O₆And (4) crystals.

The rubidium oxide as the raw material in the reaction formula may be replaced by other rubidium-containing salts such as rubidium chloride, rubidium bromide, rubidium carbonate, rubidium nitrate, rubidium oxalate, rubidium bicarbonate, rubidium hydroxide, and rubidium sulfate, the zinc oxide may be replaced by other zinc-containing salts such as zinc chloride, zinc nitrate, zinc oxalate, and zinc sulfate, and the germanium oxide may be replaced by other germanium salts.

Example 8:

with Rb₂ZnGe₂O₆Crystal preparation of nonlinear optics:

rb obtained in examples 1 to 7₂ZnGe₂O₆The nonlinear optical crystal is processed according to the crystallography data and the required size, angle and thickness, and the light-passing surface is polished, so that the nonlinear optical crystal can be used as a nonlinear optical device.

Fixing the obtained crystal at position 3 as shown in FIG. 4, and using a Q-switched Nd-YAG laser as light source at room temperature to emit infrared light with wavelength of 1064nm and infrared light beam 2 with wavelength of 1064nm to emit Rb₂ZnGe₂O₆After crystallizationGreen frequency doubling light with the wavelength of 532nm is generated, the emergent light beam 4 contains infrared light with the wavelength of 1064nm and green light with the wavelength of 532nm, and green laser with the wavelength of 532nm is obtained after passing through the filter 5.