CN113737282B - Compound zinc rubidium germanate nonlinear optical crystal, preparation method and application thereof - Google Patents

Compound zinc rubidium germanate nonlinear optical crystal, preparation method and application thereof Download PDF

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CN113737282B
CN113737282B CN202111036792.4A CN202111036792A CN113737282B CN 113737282 B CN113737282 B CN 113737282B CN 202111036792 A CN202111036792 A CN 202111036792A CN 113737282 B CN113737282 B CN 113737282B
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CN113737282A (en
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胡章贵
韩涛
李从刚
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Tianjin University of Technology
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    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
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    • C—CHEMISTRY; METALLURGY
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    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B9/00—Single-crystal growth from melt solutions using molten solvents
    • C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
    • C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
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    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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Abstract

The invention discloses a compound zinc rubidium 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 rubidium-containing compound, zinc-containing compound and germanium-containing compound raw materials, placing the raw materials in a muffle furnace, presintering at low temperature to remove moisture and gas in the raw materials, heating and calcining, taking out and grinding for many times during the period, and continuously calcining to obtain the compound zinc rubidium germanate. Further mixing the compound with a fluxing agent, heating to obtain a mixed solution, and preparing the zinc rubidium germanate nonlinear optical crystal in a crystal growth furnace. 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 zinc rubidium germanate obtained by the method can be used for preparing frequency doubling devices.

Description

Compound zinc rubidium germanate nonlinear optical crystal, preparation method and application thereof
Technical Field
The invention relates to a compound with a chemical formula of Rb 2 ZnGe 2 O 6 Zinc rubidium germanate and zinc rubidium germanate non-compoundsA linear optical crystal, a method of preparing the crystal, and a nonlinear optical device fabricated using the crystal.
Background
The nonlinear optical ((NLO) crystal can realize the conversion of laser wavelength and is a key material for preparing optical devices, and because of good stability and high laser damage threshold, the inorganic nonlinear optical crystal is applied to the fields of military, medical treatment, precision machining and communication, and currently, the second-order nonlinear optical crystal with wider application is mainly BBO (beta-BaB) 2 O 4 ) Crystal, LBO (LiB) 3 O 5 ) Crystal, KBe 2 BO 3 F 2 (KBBF) crystals and KDP (KH) 2 PO 4 ) Crystal, LN (LiNbO) 3 ) Crystals, and the like. Although the materials have great application value, the materials have some defects, such as phase change problem of BBO crystal in the growth process, deliquescence problem of CLBO and KDP crystal, lamellar growth habit and raw material virulence problem of KBBF crystal, low LN crystal laser damage threshold and the like. Along with the continuous progress and development of technology, the high and new technology has higher requirements on the nonlinear optical crystal, and the novel inorganic nonlinear optical crystal material with excellent expansion performance is particularly urgent.
The germanate crystal has excellent properties such as good stability, wide light transmission band, high damage threshold and the like, and is a candidate material for nonlinear optical crystal materials. Will d 10 Zn of electronic structure 2+ Cations and electron-transition alkali metal cations (Rb) free of d-d in the ultraviolet region + ) With GeO 4 The combination of groups aims to increase the transmission range and the frequency multiplication response of germanate. Therefore, the design and synthesis of the alkali metal zinc-containing germanate nonlinear optical crystal with excellent comprehensive performance have important significance.
Disclosure of Invention
The invention aims at providing a compound zinc rubidium germanate nonlinear optical crystal with a chemical formula of Rb 2 ZnGe 2 O 6 ；
The invention aims at providing a preparation method for synthesizing a compound zinc rubidium germanate by a solid phase reaction method and growing a nonlinear optical crystal of zinc rubidium germanate by a high-temperature melt method;
the third object of the invention is to provide the application of the zinc rubidium germanate nonlinear optical device.
The technical scheme for achieving the purpose is as follows:
the chemical formula of the compound zinc rubidium germanate provided by the invention is Rb 2 ZnGe 2 O 6 The method comprises the steps of carrying out a first treatment on the surface of the Uniformly mixing and fully grinding rubidium-containing compounds, zinc-containing compounds and germanium-containing compound raw materials, placing the mixture in a muffle furnace, presintering at low temperature to remove moisture and gas in the raw materials, heating and calcining the mixture, taking out and grinding the mixture for multiple times, and continuously calcining the mixture to obtain the compound rubidium zinc 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 solid phase reaction method is adopted to prepare the zinc rubidium germanate compound according to the following chemical reaction formula:
1)Rb 2 CO 3 +ZnO+2GeO 2 →Rb 2 ZnGe 2 O 6 +CO 2 ↑
2)2RbHCO 3 +ZnO+2GeO 2 →Rb 2 ZnGe 2 O 6 +H 2 O↑+2CO 2 ↑
3)2RbNO 3 +ZnO+2GeO 2 →Rb 2 ZnGe 2 O 6 +2NO 2 ↑+0.5O 2 ↑
4)2Rb(OH)+ZnO+2GeO 2 →Rb 2 ZnGe 2 O 6 +H 2 O↑+
5)2Rb 2 (SO 4 )+2ZnO+4GeO 2 →2Rb 2 ZnGe 2 O 6 +2SO 2 ↑+O 2 ↑
6)Rb 2 O+ZnO+2GeCl 4 +2O 2 →Rb 2 ZnGe 2 O 6 +4Cl 2 ↑
7)2RbF+ZnO+2GeO 2 +0.5O 2 →Rb 2 ZnGe 2 O 6 +F 2 ↑
8)2RbCl+ZnO+2GeO 2 +0.5O 2 →Rb 2 ZnGe 2 O 6 +Cl 2 ↑
9)2RbBr+ZnO+2GeO 2 +0.5O 2 →Rb 2 ZnGe 2 O 6 +Br 2 ↑
10)Rb 2 O+ZnO+2GeO 2 →Rb 2 ZnGe 2 O 6
11)2Rb 2 (C 2 O 4 )+2ZnO+4GeO 2 →2Rb 2 ZnGe 2 O 6 +4CO↑+O 2 ↑
12)Rb 2 CO 3 +Zn(NO 3 ) 2 +2GeO 2 →Rb 2 ZnGe 2 O 6 +CO 2 ↑+2NO 2 ↑+0.5O 2 ↑
13)Rb 2 O+Zn(NO 3 ) 2 +2GeO 2 →Rb 2 ZnGe 2 O 6 +2NO 2 ↑+0.5O 2 ↑
14)2RbNO 3 +Zn(NO 3 ) 2 +2GeO 2 →Rb 2 ZnGe 2 O 6 +4NO 2 ↑+O 2 ↑
15)2Rb(OH)+Zn(NO 3 ) 2 +2GeO 2 →Rb 2 ZnGe 2 O 6 +2NO 2 ↑+H 2 O↑+O 2 ↑
16)2RbHCO 3 +Zn(NO 3 ) 2 +2GeO 2 →Rb 2 ZnGe 2 O 6 +H 2 O↑+2CO 2 ↑+2NO 2 ↑+0.5O 2 ↑
17)Rb 2 CO 3 +Zn(Cl) 2 +0.5O 2 +2GeO 2 →Rb 2 ZnGe 2 O 6 +CO 2 ↑+Cl 2 ↑
18)Rb 2 CO 3 +ZnSO 4 +2GeO 2 →Rb 2 ZnGe 2 O 6 +CO 2 ↑+SO 2 ↑+0.5O 2 ↑
the invention provides a zinc rubidium germanate nonlinear optical crystal, the chemical formula of the compound is Rb 2 ZnGe 2 O 6 Molecular weight 238.74, without symmetry center, is an orthorhombic system, space group C222 1 The unit cell parameters are The ultraviolet cut-off edge is 315nm, and the property is stable and the ultraviolet cut-off edge is not deliquescent.
The invention provides a preparation method of a zinc rubidium germanate nonlinear optical crystal, which adopts a molten salt method to grow the zinc rubidium 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 a temperature of 850-1150 ℃ at a heating rate of 1-100 ℃/h, keeping the temperature for not less than 24 hours to obtain a mixed melt, and cooling the mixed melt to 800-1000 ℃, wherein the molar ratio of the compound zinc rubidium germanate single-phase polycrystalline powder to the fluxing agent is 1:0-15;
or directly heating the mixture of the rubidium-containing compound, the zinc-containing compound and the germanium-containing compound or the mixture of the rubidium-containing compound, the zinc-containing compound and the germanium-containing compound and the fluxing agent to 850-1150 ℃ at the heating rate of 1-100 ℃/h, keeping the temperature for not less than 24 hours to obtain mixed solution, and then cooling to 600-1000 ℃, wherein the mol 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 being essentially a self-fluxing agent, such as Rb 2 CO 3 、Rb 2 O、RbOH、RbF、RbCl、GeO 2 Salts of rubidium, germanium or complex fluxes, e.g. Rb 2 CO 3 -GeO 2 、Rb 2 O-GeO 2 、RbF-GeO 2 、RbCl-GeO 2 、Rb 2 CO 3 -TeO 2 、Rb 2 O-TeO 2 、RbF-TeO 2 、RbCl-TeO 2 、GeO 2 -TeO 2 、GeO 2 -TeO 2 -Rb 2 O、GeO 2 -TeO 2 -Rb 2 CO 3 One or more of (a) and (b).
The compound zinc rubidium germanate single-phase polycrystalline powder is prepared by adopting a solid-phase synthesis method, and comprises the 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, wherein the molar ratio of elemental rubidium in the rubidium-containing compound to elemental zinc in the zinc-containing compound to elemental germanium in the germanium-containing compound is 2:1:2, uniformly mixing the rubidium-containing compound, the zinc-containing compound and the germanium-containing compound raw materials, grinding the raw materials, putting the raw materials into a Pt crucible, placing the Pt crucible into a muffle furnace, presintering, removing moisture and gas in the raw materials, heating to 500-850 ℃, taking out and grinding for multiple times, continuously calcining, cooling to room temperature, and obtaining the compound zinc rubidium germanate single-phase polycrystalline powder.
b. B, preparing zinc rubidium germanate seed crystals, namely slowly cooling the mixed solution obtained in the step a to room temperature at the speed of 0.5-10 ℃/h, and obtaining the zinc rubidium germanate seed crystals through spontaneous crystallization;
c. placing the Pt crucible containing the mixed solution prepared in the step a into a crystal growth furnace, fixing the seed crystal obtained in the step b on a seed rod, lowering the seed crystal above the liquid level from top to bottom, preheating the seed crystal for 10-30 minutes, lowering the seed crystal into the liquid level of the solution at a temperature 5-10 ℃ higher than the saturation point, keeping the temperature for 5-10 minutes to eliminate impurities on the surface of the seed crystal, and then reducing the temperature to the saturation point temperature at a cooling rate of 1-10 ℃/min;
d. then slowly cooling at a speed of 1-5 ℃/day, and growing at a seed rod rotating speed of 5-50rpm, after the crystal grows to a required size, lifting the crystal 1cm above the liquid level, then cooling to room temperature at a speed of 10-100 ℃/h, and finally opening a hearth to take out the crystal, thereby obtaining the zinc rubidium germanate nonlinear optical crystal.
The fluxing agent Rb 2 CO 3 -GeO 2 Rb in System 2 CO 3 With GeO 2 The molar ratio of (2) is 1-4:2-6; rb (Rb) 2 O-GeO 2 Rb in System 2 O and GeO 2 The molar ratio of (2) is 1-4:2-6; rbF-GeO 2 RbF and GeO in the system 2 The molar ratio of (2) is 1-6:2-4; rbCl-GeO 2 RbCl and GeO in the system 2 The molar ratio of (2) is 1-6:2-4; rb (Rb) 2 CO 3 -TeO 2 Rb in System 2 CO 3 With TeO 2 The molar ratio of (2) is 1-3:2-6; rb (Rb) 2 O-TeO 2 Rb in System 2 O and TeO 2 The molar ratio of (2) is 1-3:2-6; rbF-TeO 2 RbF and TeO in the System 2 The molar ratio of (2) is 1-8:2-4; rbCl-TeO 2 RbCl and TeO in the system 2 The molar ratio of (2) is 1-8:2-4; geO (GeO) 2 -TeO 2 GeO in the system 2 With TeO 2 The molar ratio of (2) is 1-3:2-6; geO (GeO) 2 -TeO 2 -Rb 2 CO 3 GeO in the system 2 With TeO 2 With Rb 2 CO 3 The molar ratio of (2) is 1-3:2-4:2-6; geO (GeO) 2 -TeO 2 -Rb 2 GeO in O system 2 With TeO 2 With Rb 2 The mol 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 Rb 2 ZnGe 2 O 6 Molecular weight 238.74, without symmetry center, is an orthorhombic system, space group C222 1 The unit cell parameters are The ultraviolet cut-off edge is 315nm, and has excellent thermal stability.
Due to the use of Rb in the growth of zinc rubidium germanate nonlinear optical crystal 2 CO 3 、Rb 2 O、RbOH、RbF、RbCl、GeO 2 Self-fluxing agents or composite fluxing agents, e.g. Rb, for rubidium, germanium, etc 2 CO 3 -GeO 2 、Rb 2 O-GeO 2 、RbF-GeO 2 、RbCl-GeO 2 、Rb 2 CO 3 -TeO 2 、Rb 2 O-TeO 2 、RbF-TeO 2 、RbCl-TeO 2 、GeO 2 -TeO 2 ，GeO 2 -TeO 2 -Rb 2 O、GeO 2 -TeO 2 -Rb 2 CO 3 And the like, so that a target crystal with a larger size is easy to obtain; the obtained crystal has the advantages of excellent thermal stability, wide light transmission range, moderate hardness, stable physical and chemical properties and the like. The compound zinc rubidium germanate obtained by the method can be used for preparing a frequency doubling device, and can output green laser with the wavelength of 532nm by adopting a Nd-YAG Q-switched laser light source and infrared light with the incident wavelength of 1064nm at room temperature.
Drawings
FIG. 1 is Rb of the present invention 2 ZnGe 2 O 6 An X-ray diffraction pattern of the powder and an X-ray diffraction pattern based on a crystal structure simulation.
FIG. 2 is Rb of the present invention 2 ZnGe 2 O 6 Unit cell structure diagram.
FIG. 3 is Rb of the present invention 2 ZnGe 2 O 6 Diffuse reflectance spectrum is visible in ultraviolet light.
FIG. 4 is Rb of the present invention 2 ZnGe 2 O 6 The working principle of a nonlinear optical device for crystal manufacture is schematically shown in the specification, wherein 1 is a laser, 2 is an incident laser beam, and 3 is Rb 2 ZnGe 2 O 6 The crystal, 4, is the generated laser beam and 5 is the filter.
Detailed Description
The invention is described in detail below with reference to the attached drawings and examples:
example 1:
according to the reaction formula: rb (Rb) 2 CO 3 +ZnO+2GeO 2 →Rb 2 ZnGe 2 O 6 +CO 2 Synthesis of compound Rb 2 ZnGe 2 O 6 ；
Rb 2 CO 3 ZnO and GeO 2 Weighing according to a molar ratio of 1:1:2, placing into a mortar, uniformly mixing and grinding, and then placing into an open corundum crucible with phi 60mm multiplied by 60mmPlacing in a muffle furnace, slowly heating to 350deg.C, calcining for 24 hr, heating to 750deg.C, calcining for 24 hr, taking out, grinding, placing in the muffle furnace, heating to 800deg.C, calcining for not less than 48 hr to obtain single-phase polycrystalline powder of zinc rubidium germanate, and analyzing by powder X-ray diffraction test to obtain sample powder X-ray spectrogram and zinc rubidium germanate Rb 2 ZnGe 2 O 6 The theoretical X-ray spectrograms obtained by the single crystal structure are consistent, see figure 1;
the prepared compound zinc rubidium germanate Rb 2 ZnGe 2 O 6 Single phase polycrystalline powder and fluxing agent RbF-GeO 2 In molar ratio Rb 2 ZnGe 2 O 6 :RbF-GeO 2 =1:3, wherein RbF and GeO 2 The molar ratio of (2) is 4:1, the materials are mixed uniformly, pressed, filled into a Pt crucible with phi 60mm multiplied by 60mm, the mixed raw materials are heated to 850 ℃ at the heating rate of 10-100 ℃/h, the temperature is kept for not less than 24 hours, the melt is mixed uniformly, meanwhile, pt wires are put into the liquid surface, and then the temperature is reduced to induce spontaneous crystallization; the chemical formula of the crystal is Rb 2 ZnGe 2 O 6 Molecular weight 238.74, without symmetry center, is an orthorhombic system, space group C222 1 The unit cell parameters are The ultraviolet cut-off edge is 315nm, and the ultraviolet cut-off edge has stable property and no deliquescence, and is shown in fig. 2 and 3.
Slowly cooling the melt at a rate of 1-5 ℃/h to obtain zinc rubidium germanate seed crystals;
growing crystals in a compound melt: rb obtained by spontaneous crystallization 2 ZnGe 2 O 6 The small crystal grain is used as seed crystal, the seed crystal is fixed on a seed crystal rod by utilizing a platinum wire, the seed crystal is firstly placed at a position 1-2cm above the liquid level for preheating treatment, then the seed crystal is immersed below the liquid level at the temperature 5-10 ℃ higher than the saturation point, the surface impurities are removed after the seed crystal is kept for 5-10 minutes, and then the temperature is quickly reduced to the saturation point temperature;
cooling at 1-3deg.C/day, rotating seed rod at 5-50rpm, lifting the crystal 1cm above liquid surface, cooling to room temperature at 10-50deg.C/hr, and taking out the crystal to obtain Rb 2 ZnGe 2 O 6 And (5) a crystal.
The raw material rubidium carbonate in the reaction formula can be replaced by other rubidium-containing salts such as rubidium oxide, rubidium chloride, rubidium bromide, rubidium nitrate, rubidium oxalate, rubidium hydroxide, rubidium bicarbonate, rubidium sulfate and the like, zinc oxide can be replaced by other zinc-containing salts such as zinc chloride, zinc nitrate, zinc oxalate, zinc sulfate and the like, and germanium oxide is replaced by other germanium salts.
Example 2:
according to the reaction formula: 2RbNO 3 +ZnO+2GeO 2 →Rb 2 ZnGe 2 O 6 +2NO 2 ↑+0.5O 2 Synthesis of compound Rb 2 ZnGe 2 O 6 ；
RbNO 3 ZnO and GeO 2 Directly weighing raw materials according to a molar ratio of 2:1:2, and mixing the weighed raw materials with a fluxing agent Rb 2 O-GeO 2 Mixing according to a molar ratio of 1:3, wherein Rb 2 O and GeO 2 The molar ratio of (2) is 4:1, the mixture is put into a platinum crucible with phi 60mm multiplied by 60mm, the temperature is raised to 950 ℃, the temperature is kept for at least 24 hours, so that the melt is uniformly mixed, meanwhile, pt wires are put in, and then the temperature is reduced to induce spontaneous crystallization;
slowly cooling at a cooling rate of 1-5 ℃/h, and spontaneously crystallizing to obtain zinc rubidium germanate seed crystals;
growing crystals in a compound melt: rb obtained by spontaneous crystallization 2 ZnGe 2 O 6 The small crystal grain is used as seed crystal, the seed crystal is fixed on a seed crystal rod by utilizing a platinum wire, the seed crystal is firstly placed at a position 1-2cm above the liquid level for preheating treatment, then the seed crystal is immersed below the liquid level at the temperature 5-10 ℃ higher than the saturation point, the surface impurities are removed after the seed crystal is kept for 5-10 minutes, and then the temperature is quickly reduced to the saturation point temperature;
then cooling at the rate of 1-3 ℃/day, the rotating speed of the seed rod is 5-50rpm, after the crystal growth is finished, lifting the crystal to the liquid level, cooling to room temperature at the rate of 10-50 ℃/h, and taking the crystal from the hearthTaking out the crystal to obtain Rb 2 ZnGe 2 O 6 And (5) a crystal.
The raw material rubidium nitrate in the reaction formula can be replaced by other rubidium-containing salts such as rubidium oxide, rubidium chloride, rubidium bromide, rubidium carbonate, rubidium oxalate, rubidium hydroxide, rubidium bicarbonate, rubidium sulfate and the like, zinc oxide can be replaced by other zinc-containing salts such as zinc chloride, zinc nitrate, zinc oxalate, zinc sulfate and the like, and germanium oxide is replaced by other germanium salts.
Example 3:
according to the reaction formula: 2Rb (OH) +ZnO+2GeO 2 →Rb 2 ZnGe 2 O 6 +H 2 O ≡synthetic compound Rb 2 ZnGe 2 O 6 ；
Rb (OH), znO and GeO 2 Directly weighing raw materials according to a molar ratio of 2:1:2, and mixing the weighed raw materials with a fluxing agent RbF-TeO 2 Mixing according to a molar ratio of 1:3, wherein RbF and TeO 2 The molar ratio of (2) is 3:1, the mixture is put into a platinum crucible with phi 60mm multiplied by 60mm, the temperature is raised to 900 ℃, the temperature is kept for at least 24 hours, so that the melt is uniformly mixed, meanwhile, pt wires are put in, and then the temperature is reduced to induce spontaneous crystallization;
slowly cooling the melt at a rate of 1-5 ℃/h to obtain zinc rubidium germanate seed crystals;
growing crystals in a compound melt: rb obtained by spontaneous crystallization 2 ZnGe 2 O 6 The small crystal grain is used as seed crystal, the seed crystal is fixed on a seed crystal rod by utilizing a platinum wire, the seed crystal is firstly placed at a position 1-2cm above the liquid level for preheating treatment, then the seed crystal is immersed below the liquid level at the temperature 5-10 ℃ higher than the saturation point, the surface impurities are removed after the seed crystal is kept for 5-10 minutes, and then the temperature is quickly reduced to the saturation point temperature;
cooling at a rate of 1-3deg.C/day, rotating the seed rod at 5-50rpm, removing the crystal from the liquid surface after crystal growth, cooling to room temperature at a rate of 10-50deg.C/hr, and taking out the crystal from the furnace to obtain Rb 2 ZnGe 2 O 6 And (5) a crystal.
The raw material rubidium hydroxide 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 hydrogen carbonate, rubidium sulfate and the like, zinc oxide can be replaced by other zinc-containing salts such as zinc chloride, zinc nitrate, zinc oxalate, zinc sulfate and the like, and germanium oxide is replaced by other germanium salts.
Example 4:
according to the reaction formula: 2Rb 2 SO 4 +2ZnO+4GeO 2 →2Rb 2 ZnGe 2 O 6 +2SO 2 ↑+O 2 Synthesis of compound Rb 2 ZnGe 2 O 6 ；
Rb 2 (SO 4 )，ZnO，GeO 2 Directly weighing raw materials according to a molar ratio of 1:1:2, and mixing the weighed raw materials with a fluxing agent GeO 2 -TeO 2 Mixing according to a molar ratio of 1:3, wherein GeO 2 With TeO 2 The mixture is put into a platinum crucible with phi 60mm multiplied by 60mm, the temperature is raised to 900 ℃ and the constant temperature is kept for not less than 24 hours, so that the melt is uniformly mixed, meanwhile, pt wires are put in, and then the temperature is reduced to induce spontaneous crystallization;
slowly cooling the melt at a rate of 1-5 ℃/h to obtain zinc rubidium germanate seed crystals;
growing crystals in a compound melt: rb obtained by spontaneous crystallization 2 ZnGe 2 O 6 The small crystal grain is used as seed crystal, the seed crystal is fixed on a seed crystal rod by a platinum wire, the seed crystal is firstly placed at a position 1-2cm above the liquid level for preheating treatment, then the seed crystal is immersed below the liquid level at the temperature 5 ℃ higher than the saturation point, the seed crystal is kept for 10 minutes to remove surface impurities, and then the temperature is quickly reduced to 850 ℃;
cooling at a rate of 1-3deg.C/day, rotating the seed rod at 5-50rpm, removing the crystal from the liquid surface after crystal growth, cooling to room temperature at a rate of 10-50deg.C/hr, and taking out the crystal from the furnace to obtain Rb 2 ZnGe 2 O 6 And (5) a crystal.
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 hydrogen carbonate, rubidium hydroxide and the like, zinc oxide can be replaced by other zinc-containing salts such as zinc chloride, zinc nitrate, zinc oxalate, zinc sulfate and the like, and germanium oxide is replaced by other germanium salts.
Example 5:
according to the reaction formula: 2RbCl+ZnO+2GeO 2 +0.5O 2 →Rb 2 ZnGe 2 O 6 +Cl 2 Synthesis of compound Rb 2 ZnGe 2 O 6 ；
RbCl, znO, geO 2 Directly weighing raw materials according to a molar ratio of 2:1:2, and mixing the weighed raw materials with a fluxing agent RbF-TeO 2 Uniformly mixing according to a molar ratio of 1:2, wherein RbF and TeO 2 The molar ratio of (2) is 3:1, the mixture is put into a platinum crucible with phi 60mm multiplied by 60mm, the temperature is raised to 850 ℃, the temperature is kept for at least 24 hours, so that the melt is uniformly mixed, meanwhile, pt wires are put in, and then the temperature is reduced to induce spontaneous crystallization;
slowly cooling the melt at a rate of 1-5 ℃/h to obtain zinc rubidium germanate seed crystals;
growing crystals in a compound melt: rb obtained by spontaneous crystallization 2 ZnGe 2 O 6 The small crystal grain is used as seed crystal, the seed crystal is fixed on a seed crystal rod by utilizing a platinum wire, the seed crystal is firstly placed at a position 1-2cm above the liquid level for preheating treatment, then the seed crystal is immersed below the liquid level at the temperature 5-10 ℃ higher than the saturation point, the surface impurities are removed after the seed crystal is kept for 5-10 minutes, and then the temperature is quickly reduced to the saturation point temperature;
cooling at a rate of 1-3deg.C/day, rotating the seed rod at 5-50rpm, removing the crystal from the liquid surface after crystal growth, cooling to room temperature at a rate of 10-50deg.C/hr, and taking out the crystal from the furnace to obtain Rb 2 ZnGe 2 O 6 And (5) a crystal.
The raw material rubidium chloride in the reaction formula can be replaced by other rubidium-containing salts such as rubidium oxide, rubidium bromide, rubidium carbonate, rubidium nitrate, rubidium oxalate, rubidium bicarbonate, rubidium hydroxide, rubidium sulfate and the like, zinc oxide can be replaced by other zinc-containing salts such as zinc chloride, zinc nitrate, zinc oxalate, zinc sulfate and the like, and germanium oxide is replaced by other germanium salts.
Example 6:
according to the reaction formula: 2RbBr+ZnO+2GeO 2 +0.5O 2 →Rb 2 ZnGe 2 O 6 +Br 2 Synthesis of compound Rb 2 ZnGe 2 O 6 ；
RbBr, znO, geO 2 Directly weighing raw materials according to a molar ratio of 2:1:2, and mixing the weighed raw materials with a fluxing agent RbF-TeO 2 Uniformly mixing according to a molar ratio of 1:2, wherein RbF and TeO 2 The molar ratio of (2) is 3:1, the mixture is put into a platinum crucible with phi 60mm multiplied by 60mm, the temperature is raised to 850 ℃, the temperature is kept for at least 24 hours, so that the melt is uniformly mixed, meanwhile, pt wires are put in, and then the temperature is reduced to induce spontaneous crystallization;
slowly cooling the melt at a rate of 1-5 ℃/h to obtain zinc rubidium germanate seed crystals;
growing crystals in a compound melt: rb obtained by spontaneous crystallization 2 ZnGe 2 O 6 The small crystal grain is used as seed crystal, the seed crystal is fixed on a seed crystal rod by utilizing a platinum wire, the seed crystal is firstly placed at a position 1-2cm above the liquid level for preheating treatment, then the seed crystal is immersed below the liquid level at the temperature 5-10 ℃ higher than the saturation point, the surface impurities are removed after the seed crystal is kept for 5-10 minutes, and then the temperature is quickly reduced to the saturation point temperature;
cooling at a rate of 1-3deg.C/day, rotating the seed rod at 5-50rpm, removing the crystal from the liquid surface after crystal growth, cooling to room temperature at a rate of 10-50deg.C/hr, and taking out the crystal from the furnace to obtain Rb 2 ZnGe 2 O 6 And (5) a crystal.
The raw material rubidium bromide in the reaction formula can be replaced by other rubidium-containing salts such as rubidium oxide, rubidium chloride, rubidium carbonate, rubidium nitrate, rubidium oxalate, rubidium bicarbonate, rubidium hydroxide, rubidium sulfate and the like, zinc oxide can be replaced by other zinc-containing salts such as zinc chloride, zinc nitrate, zinc oxalate, zinc sulfate and the like, and germanium oxide is replaced by other germanium salts.
Example 7:
according to the reaction formula: rb (Rb) 2 O+ZnO+2GeO 2 →Rb 2 ZnGe 2 O 6 Synthesis of Compound Rb 2 ZnGe 2 O 6 ；
Rb 2 O, znO and GeO 2 Directly weighing raw materials according to a molar ratio of 1:1:2, and mixing the weighed raw materials with a fluxing agent GeO 2 -TeO 2 -Rb 2 O is uniformly mixed according to the mol ratio of 1:1, wherein GeO is 2 With TeO 2 With Rb 2 The molar ratio of O is 1:2:2, the mixture is put into a platinum crucible with phi 60mm multiplied by 60mm, the temperature is raised to 950 ℃, so that the melt is uniformly mixed, pt wires are simultaneously put in, and then the temperature is reduced to induce spontaneous crystallization;
slowly cooling the melt at a rate of 1-5 ℃/h to obtain zinc rubidium germanate seed crystals;
growing crystals in a compound melt: rb obtained by spontaneous crystallization 2 ZnGe 2 O 6 The small crystal grain is used as seed crystal, the seed crystal is fixed on a seed crystal rod by utilizing a platinum wire, the seed crystal is firstly placed at a position 1-2cm above the liquid level for preheating treatment, then the seed crystal is immersed below the liquid level at the temperature 5-10 ℃ higher than the saturation point, the surface impurities are removed after the seed crystal is kept for 5-10 minutes, and then the temperature is quickly reduced to the saturation point temperature;
cooling at a rate of 1-3deg.C/day, rotating the seed rod at 5-50rpm, removing the crystal from the liquid surface after crystal growth, cooling to room temperature at a rate of 10-50deg.C/hr, and taking out the crystal from the furnace to obtain Rb 2 ZnGe 2 O 6 And (5) a crystal.
The raw material rubidium oxide in the reaction formula can be replaced by other rubidium-containing salts such as rubidium chloride or rubidium bromide or rubidium carbonate or rubidium nitrate or rubidium oxalate or rubidium bicarbonate or rubidium hydroxide or rubidium sulfate, the zinc oxide can be replaced by other zinc-containing salts such as zinc chloride or zinc nitrate or zinc oxalate or zinc sulfate, and the germanium oxide is replaced by other germanium salts.
Example 8:
using Rb 2 ZnGe 2 O 6 Crystal preparation nonlinear optics:
rb obtained in examples 1 to 7 2 ZnGe 2 O 6 The nonlinear optical crystal is subjected to crystal processing according to the crystallographic data and the required size, angle and thickness, and the light-passing surface is subjected to polishing treatment, so that the nonlinear optical crystal can be used as a nonlinear optical device.
The obtained crystal was fixed at the 3 position as shown in FIG. 4, and at room temperature, a Q-switched Nd: YAG laser was used as a light source, an infrared light having a wavelength of 1064nm was incident, and an infrared light beam 2 having a wavelength of 1064nm was incident on Rb 2 ZnGe 2 O 6 After the crystal, a wave is generatedThe green frequency multiplication light with the length of 532nm, the emergent light beam 4 contains infrared light with the wavelength of 1064nm and green light with the wavelength of 532nm, and the green laser with the wavelength of 532nm is obtained after passing through the filter 5.

Claims (5)

1. The preparation method of the compound zinc rubidium germanate nonlinear optical crystal is characterized by comprising the following steps:
a. uniformly mixing the compound zinc rubidium germanate single-phase polycrystalline powder with a fluxing agent, heating the mixture to a temperature of 850-1150 ℃ at a heating rate of 1-100 ℃/h, keeping the temperature for not less than 24 hours to obtain a mixed melt, and cooling the mixed melt to 800-1000 ℃, wherein the molar ratio of the compound zinc rubidium germanate single-phase polycrystalline powder to the fluxing agent is 1:0-15;
or directly heating the mixture of the rubidium-containing compound, the zinc-containing compound and the germanium-containing compound or the mixture of the rubidium-containing compound, the zinc-containing compound and the germanium-containing compound and the fluxing agent to 850-1150 ℃ at the heating rate of 1-100 ℃/h, keeping the temperature for not less than 24 hours to obtain mixed solution, and then cooling to 600-1000 ℃, wherein the mol 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;
mixing a rubidium compound, a zinc compound and a germanium compound, preparing rubidium zinc germanate by a solid phase reaction method, wherein the molar ratio of elemental rubidium in the rubidium compound to elemental zinc in the zinc compound to elemental germanium in the germanium compound is 2:1:2, uniformly mixing the rubidium compound, the zinc compound and the germanium compound raw materials, grinding, placing the mixture into a Pt crucible, placing the Pt crucible into a muffle furnace, presintering to remove moisture and gas in the raw materials, heating to 500-850 ℃, taking out and grinding for a plurality of times, continuously calcining for at least 72 hours, and cooling to room temperature to obtain the compound rubidium germanate single-phase polycrystalline powder;
b. b, preparing zinc rubidium germanate seed crystals, namely slowly cooling the mixed solution obtained in the step a to room temperature at the speed of 0.5-10 ℃/h, and obtaining the zinc rubidium germanate seed crystals through spontaneous crystallization;
c. placing the Pt crucible containing the mixed solution prepared in the step a into a crystal growth furnace, fixing the seed crystal obtained in the step b on a seed rod, lowering the seed crystal above the liquid level from top to bottom, preheating the seed crystal for 10-30 minutes, lowering the seed crystal into the liquid level of the solution at a temperature 5-10 ℃ higher than the saturation point, keeping the temperature for 5-10 minutes to eliminate impurities on the surface of the seed crystal, and then reducing the temperature to the saturation point temperature at a cooling rate of 1-10 ℃/min;
d. slowly cooling at a speed of 1-5 ℃/day, and growing at a seed rod rotating speed of 5-50rpm, lifting the crystal 1cm above the liquid surface after the crystal grows to a required size, then cooling to room temperature at a speed of 10-100 ℃/h, and finally opening a hearth to take out the crystal to obtain the zinc rubidium germanate nonlinear optical crystal;
the obtained crystal has the chemical formula of Rb 2 ZnGe 2 O 6 Molecular weight 238.74, without symmetry center, is an orthorhombic system, space group C222 1 The unit cell parameters are The ultraviolet cut-off edge of the compound is 315nm.
2. The method for preparing the compound zinc rubidium germanate nonlinear optical crystal according to claim 1, which is characterized in that: the fluxing agent is one of rubidium hydroxide, germanium hydroxide, rubidium oxide, germanium oxide, rubidium salt, germanium salt, lead oxide or composite fluxing agent, wherein the composite fluxing agent is Rb 2 O-GeO 2 、RbF-GeO 2 、RbF-TeO 2 、Rb 2 O-TeO 2 、GeO 2 -TeO 2 Or GeO 2 -TeO 2 -Rb 2 One of O.
3. The method for preparing the compound zinc rubidium germanate nonlinear optical crystal according to claim 2, wherein the compound fluxing agent Rb 2 O-GeO 2 Rb in System 2 O and GeO 2 The molar ratio of (2) is 1-4:2-6; rbF-GeO 2 RbF and GeO in the system 2 The molar ratio of (2) is 1-6:2-4; rb (Rb) 2 O-TeO 2 Rb in System 2 O and TeO 2 The molar ratio of (2) is 1-3:2-6; rbF-TeO 2 RbF and TeO in the System 2 The molar ratio of (2) is 1-8:2-4; geO (GeO) 2 -TeO 2 GeO in the system 2 With TeO 2 The molar ratio of (2) is 1-3:2-6; geO (GeO) 2 -TeO 2 -Rb 2 GeO in O system 2 With TeO 2 With Rb 2 The molar ratio of O is 1-3:2-4:2-6.
4. Use of the zinc rubidium germanate nonlinear optical crystal obtained by the preparation method according to any one of claims 1-3, wherein the zinc rubidium germanate nonlinear optical crystal is used for manufacturing a frequency multiplication generator, an upper frequency converter, a lower frequency converter and an optical parametric oscillator.
5. The compound zinc rubidium germanate nonlinear optical crystal is characterized in that: prepared by the process of any one of claims 1-3, the compound having the formula Rb 2 ZnGe 2 O 6 Molecular weight 238.74, without symmetry center, is an orthorhombic system, space group C222 1 The unit cell parameters are The ultraviolet cut-off edge of the compound is 315nm.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101984151A (en) * 2010-11-22 2011-03-09 中国科学院新疆理化技术研究所 Di lithium tetra borate rubidium nonlinear optic crystal, preparation method and application thereof
CN105332052A (en) * 2014-08-08 2016-02-17 中国科学院新疆理化技术研究所 Compound rubidium sodium chloroborate, and rubidium sodium chloroborate optical crystal and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101984151A (en) * 2010-11-22 2011-03-09 中国科学院新疆理化技术研究所 Di lithium tetra borate rubidium nonlinear optic crystal, preparation method and application thereof
CN105332052A (en) * 2014-08-08 2016-02-17 中国科学院新疆理化技术研究所 Compound rubidium sodium chloroborate, and rubidium sodium chloroborate optical crystal and preparation method and application thereof

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
K2Sn2ZnSe6, Na2Ge2ZnSe6, and Na2In2GeSe6: a new series of quaternary selenides with intriguing structural diversity and nonlinear optical properties;Molin Zhou ect.;The Royal Society of Chemistry;第45卷;第7627–7633页 *
Mahiaoui, R. ect..Electronic, bonding, linear, and nonlinear optical properties of Na2MGe2Q6 (M=Cd, Zn, Hg *
Phase analysis and ionic conductivity studies of the sodium zinc germanium oxide (Na2ZnGeO4)-sodium zinc germanium oxide (Na2ZnGe2O6) system;Grins, Jekabs etc.;Solid State Ionics;第869-876页 *
Q=S, Se), Na2ZnSi2S6, and Na2ZnSn2S6 two metal-mixed chalcogenide compounds: Insights from an ab initio study.Journal of Physics and Chemistry of Solids.2018,第119卷第220-227页. *
The crystal structure and ionic conductivity properties of potassium zinc germanate (K2ZnGe2O6);Grins Jekabs etc.;Acta Chemica Scandinavica;第43卷(第01期);第11-14页 *
尚世铉 等.《近代物理实验技术 2》.北京：高等教育出版社,1993,(第1版),第461-462页. *

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