CN100564256C - The synthetic method of the uniform spherical doped polycrystalline lithium niobate material of composition - Google Patents

The synthetic method of the uniform spherical doped polycrystalline lithium niobate material of composition Download PDF

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CN100564256C
CN100564256C CNB2007100156753A CN200710015675A CN100564256C CN 100564256 C CN100564256 C CN 100564256C CN B2007100156753 A CNB2007100156753 A CN B2007100156753A CN 200710015675 A CN200710015675 A CN 200710015675A CN 100564256 C CN100564256 C CN 100564256C
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lithium niobate
niobium
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CN101066761A (en
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王继扬
姚淑华
刘宏
郑斐斐
颜涛
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Shandong University
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Abstract

The present invention relates to the synthetic method of the uniform spherical doped polycrystalline lithium niobate material of a kind of composition, belong to field of inorganic material preparing technology.This method is containing carboxylic acid group's organic solvent uniform mixing with niobium source raw material, forms to contain the niobium title complex, calculates the accurate amount of niobium, the Li of Jia Ruing again by the method for thermogravimetric analysis +, MgO, ZnO or HfO 2, magnetic agitation realizes the uniform mixing of doped element and substrate material atomic level, and solution is adopted the spray drying granulation technology, realizes the control to the polycrystal particle diameter, calcination is synthetic to have certain particle diameter polycrystal being lower than under the solid state reaction temperature.The present invention is raw materials used to be conventional material, mixes in solution and can help improving the crystalline homogeneity, and can control particle diameter, widens the range of application of crystal growth.

Description

The synthetic method of the uniform spherical doped polycrystalline lithium niobate material of composition
(1) technical field
The present invention relates to the synthetic method of the uniform spherical doped polycrystalline lithium niobate material of a kind of composition, belong to field of inorganic material preparing technology.
(2) background technology
Lithium niobium trioxide is a kind of good multi-functional crystal, has good piezoelectric property, non-linear optical property, electric light and photorefractive property etc.Can be used to make various difference in functionality devices, such as: infrared eye, laser modulator, optical switch, optical parametric oscillator, integrated optical element, high-frequency wideband wave filter, high-frequency high temperature transverter, little acoustic device, laser frequency multiplier, self-frequency-doubling laser, optical dioptric device (as high-resolution Hologram Storage) etc.Because the lithium niobate crystals applied range, consumption is big, and the production of lithium niobate crystals has had very big scale in the world.The Lithium niobium trioxide industrial scale has really become a kind of crystal of industrialization in hundred tons every year in the world.Because the singularity of Lithium Oxide 98min columbium monoxide phasor, the crystal that adopts general growth technique to obtain is Li/Nb ratio (mol ratio) (Li 2O/Nb 2O 5) be the non-stoichiometric crystal of 48.6/51.4.Itself inherent defective makes it can only be used for the piezoelectricity purposes.Can obtain to have the optical grade lithium niobate crystals of optical applications by doping and strict control growing technology.
Because lithium niobate crysal with near stoichiometric ratio is the monocrystalline of the less natural single domain of defective, have a lot of superiority and a purposes widely, so, become the emphasis of Study on Crystals Growth and exploitation in the world.
The lithium niobate crysal with near stoichiometric ratio of doped with magnesia, zinc oxide, hafnia etc. is compared with doped with magnesia or the congruent lithium niobate crystals of zinc oxide with general chemistry metering ratio lithium niobate crystal, because higher light injury threshold is arranged, can realize noncritical phase matching under the room temperature, the farmland turnover voltage is lower, it is wide to see through wavelength band, advantages such as electric light and non-linear capable characteristic are better have more wide application prospect.
Containing transition metal ion and rare earth ion in lithium niobate crystals are sold off process thereby influence light, and light is sold off ability and improved, and make having a extensive future of the application change of doped crystal aspect Hologram Storage.
Through the effort of decades, congruent lithium niobate crystals has been realized growth in batches in China, and the growing technology of lithium niobate crysal with near stoichiometric ratio has also reached the level of mass production.But the growth technique of doped lithium columbate crystal remains technological difficulties.When in congruent or stoichiometric ratio lithium niobate crystal, mixing other element, major defects such as inclusion, macroscopic scattering particles often appear in process of growth, cause the crystal optics lack of homogeneity, can utilize part low, cost improves, and has seriously hindered the mass production process of doped crystal and has gathered the flow of research of sheet multidomain laser apparatus and massage storage as the high quality of material.Applicant's experimental study for many years shows that the source of these defectives mainly is because the doped element Local enrichment in melt in the sintered material causes.
At present, the polycrystal raw material of doping optical level and lithium niobate crysal with near stoichiometric ratio growth generally adopts the method for solid state reaction to synthesize.Synthesis technique commonly used is, the oxidate powder powder stock of commercially available Quilonum Retard, Niobium Pentxoxide and doped element is carried out dry mixed, calcines syntheticly at 1100-1150 ℃, obtains the doped polycrystalline material.In building-up process, easy reaction obtains Lithium niobium trioxide although Niobium Pentxoxide (1480 ℃ of fusing points) and Quilonum Retard decompose the Lithium Oxide 98min that obtains, because the doping very low (1-5mol%) and the very high (magnesium oxide: 2800 ℃ of fusing point of doping oxides such as magnesium oxide, zinc oxide, hafnia; Zinc oxide: 1975 ℃; Hafnia: 2812 ℃), its reactive behavior is low, and velocity of diffusion is also lower in Lithium niobium trioxide, is difficult to form even adulterated polycrystalline lithium niobate material.Because the doped polycrystalline material after the granularity of general commercially available doping oxide at micron or submicron order, is synthesized is insufficient because of reaction, and causes the doped element skewness, even still has particles such as magnesium oxide or zinc oxide.This uneven polycrystal raw material can form the melt cluster of hyperoxia magnesium not of uniform size or heightization zinc etc. in melt in fusing and crystal growing process; even still exist with the form of solid phase particles; finally the form with scattering particles or inclusion is present in the crystal, when serious even directly influence crystal growing process.If in building-up process, further improve temperature of reaction,, can cause sintered material sintering even fusing to be difficult to fragmentation or Li although might improve implant uniformity 2O volatilizees in a large number and feed composition is departed from.If improve the homogeneity that doped element distributes by improving the melt temperature of fusion and prolonging soaking time in melt, can cause Li equally 2A large amount of volatilizations of O cause departing from of the interior composition of melt.So the processing parameter of regulating in solid phase synthesis process and the process of growth all can not solve the growth defect problem that occurs in the doped lithium columbate crystal process of growth.How solving this technology difficult problem has become pendulum to press for the problem of solution most in our front.
In addition, along with the development of technology, the demand of large-size crystals is increasing, and specification of quality is also more and more higher.Traditional handle system can not satisfy the needs of crystal growth fully, must improve crystal growth system.In recent years, along with the development of crystal technique, diversified automatic continuous feeding has been applied for patent in succession, and is used for the crystal of growing large-size.Automatically the used polycrystal of continuous charging often needs certain fluidity again, must melt immediately after entering the fusion melt.The polycrystal granularity of tradition solid phase synthesis is inhomogeneous, and is mobile poor, and therefore the fusing point height, changes warm field gradient after entering melt easily, makes the decline of growth interface temperature local overcooling occur, makes crystal growth be difficult to carry out smoothly.Therefore, need synthetic globular polycrystal, to realize strict quantitative self-feeding process with epigranular, good fluidity.Common solid phase synthesis process can't satisfy this requirement.
Chemical synthesis process solves the preferred approach of Lithium niobium trioxide raw material doping problem of non-uniform beyond doubt.Owing to be difficult to be contained simultaneously the mixing solutions of niobium, lithium, magnesium or zine ion, so far, also do not find any relevant document that adopts chemical method synthesizing blender polycrystalline lithium niobate material.Japan Emerson (Chem.Mater, 2001,13:1905-1909) waiting the people is raw material with niobium chloride and lithium hydroxide, is that complexing agent has only synthesized LiNbO with chemical method with the oxysuccinic acid 3Powder, this method are with the synthetic Lithium niobium trioxide powder of calcining behind the mixing solutions heating evaporation.This method can't realize still can't realizing the doping of high-melting-point raw materials such as magnesium oxide or zinc oxide.In addition, the heating evaporation speed of solution is slow, and is not easy control, is difficult to realize the batch process of raw material.And because this method can't realize the control to synthesised polycrystalline powder particle form and particle diameter, the powder that obtains is not suitable for the crystal growth of continuous charging.
(3) summary of the invention
The present invention is directed to the deficiencies in the prior art, propose the synthetic method of the uniform spherical doped polycrystalline lithium niobate material of a kind of composition, can obtain the uniform spherical doped polycrystalline lithium niobate material of composition, cryochemistry is synthetic, saves the energy.
The synthetic method of the uniform spherical doped polycrystalline lithium niobate material of a kind of composition, step is as follows:
(1) with niobium source raw material Nb (OH) 5Be dissolved in 36% concentrated hydrochloric acid (m/m) or NbCl 5The Nb that obtains soluble in water 2O 5NH 2O.Under the magnetic agitation to Nb 2O 5NH 2Add the organic solvent that contains the carboxylic acid group, Nb among the O 5+With the organic solvent mol ratio be 1: 2～3.Magnetic agitation 30～40min, with ammoniacal liquor regulator solution pH to 7-8, formation contains the niobium title complex;
(2) calculate the accurate amount of niobium by the method for thermogravimetric analysis
The solution of getting step (1) gained is a small amount of, and at 700 ℃ of calcining 2h, weighing obtains the solution measured concentration and be: the Nb of unit 2O 5/ g solution calculates the Nb in step (1) solution 5+Accurate amount;
(3) Nb that obtains according to step (2) 5+Accurate amount, calculate Li by following equation +, MO or MO 2Accurate amount,
Li ++0.05MO+0.49Nb 2O 5→LiNb 0.98M 0.05O 3，I
MO is a hotchpotch among the formula I, specifically is selected from MgO or ZnO.
Li ++0.05MO 2+0.48Nb 2O 5→LiNb 0.96M 0.05O 3，II
MO among the formula II 2Be hotchpotch, specifically be selected from HfO 2
The LiOHH that in the solution of step (1) gained, adds by calculated amount 2O or Li 2CO 3, MgO, ZnO or HfO 2, magnetic agitation is to dissolving, thus the uniform mixing of realization doped element and substrate material atomic level;
(4) step (3) is obtained mixing solutions and carry out spraying drying, remove moisture, obtain spheric granular precursor shape raw material;
(5) the presoma powder is calcined 4-6h down at 600-800 ℃, get spheric doped lithium columbate raw material.
Need to prove that step (1) niobium source raw material is a growing crystal niobium source raw material commonly used, the present invention is not particularly limited, but preferred niobium source raw material is Nb (OH) 5Or NbCl 5
Nb (OH) in the step (1) 5The mass volume ratio that is dissolved in 36% concentrated hydrochloric acid is 1g: 5～10ml, NbCl 5Mass volume ratio soluble in water is 1g: 10～20ml.
The preferred 30%v/v ammoniacal liquor of ammoniacal liquor in the step (1).Ammoniacal liquor regulator solution pH=7-8 helps obtaining the discharge of settled solution and chlorion.
The organic solvent that contains the carboxylic acid group described in the step (1) specifically is selected from oxyacetic acid, lactic acid, oxysuccinic acid, citric acid, amygdalic acid, oxalic acid or tartrate etc.Wherein, preferred DL-oxysuccinic acid (C 4H 6O 5, write a Chinese character in simplified form DL-MA) or citric acid (C 6H 8O 7, write a Chinese character in simplified form CA).
The amount of the solution of getting is not particularly limited during step (2) thermogravimetric analysis.
Select sintering temperature at 600-800 ℃ in the step (5), this sintering temperature helps the generation of doped polycrystalline lithium niobate material thing phase most.
The spray drying technology that the present invention adopts combining nano materials such as easy available niobium hydroxide, Quilonum Retard, lithium hydroxide, magnesium oxide, zinc chloride, hafnia on the market to use always in solution chemistry synthetic technology commonly used and chemical industry and the Production of Ceramics in synthetic, synthesizing blender polycrystalline lithium niobate material, not only can solve the defect problem that uneven doped elements in the polycrystal causes growing crystal, and can prepare spherical polycrystalline powder, improve the flowability of polycrystal raw material.Its principle is the composite precursor that obtains high dispersing by title complex and the mating reaction of different metal ionic, removes organic ligand by the pyrolysated method and obtains.Make the water-soluble or organic solvent formation mixing solutions of various insoluble component in the raw material by the number of chemical method, thereby realize the uniform mixing of doped element and substrate material atomic level,, realize control the polycrystal particle diameter by solution is carried out spraying drying.Adopt the inventive method can be under than the temperature of low 400 ℃ of common solid-phase synthesis the uniform polycrystal of synthesizing blender, institute's synthetic raw material is a spherical particle, helps the accurate control of the feed rate in the continuous charging process.
The present invention adopts the synthetic even adulterated polycrystal with certain particle size of chemical method, and the primary granule size of the polycrystal that burns till is at nanoscale, and its fusing point is starkly lower than the solid state reaction polycrystal.Simultaneously, the fusing point that is used for the synthesised polycrystalline material reduces, in the crystal growing process, not only can save the energy, and for the continuous charging growth technique, can prevent to realize the automatization of doping stoichiometric ratio lithium niobate crystal growth because the adding of polycrystal causes floating brilliant phenomenon in the process of growth.
(4) description of drawings
Fig. 1 is the Nb that produces when adopting the inventive method thermogravimetric 2O 5X-ray diffracting spectrum;
Fig. 2 is the X-ray diffracting spectrum of the MgO:SLN of the inventive method preparation.
(5) embodiment
Embodiment 1:
Synthesizing of MgO (5mol%) stoichiometric proportion lithium niobate polycrystal
1. take by weighing Nb (OH) 52.460g obtain active stronger Nb with concentrated hydrochloric acid 12ml heating for dissolving 2O 5NH 2O adds DL-oxysuccinic acid (C 4H 6O 5, DL-MA) 2.674g is adjusted to pH=7 with ammoniacal liquor (30%), and filtration can obtain clear Nb-MA solution.
2. utilize the actual concentration of thermogravimetric analysis test soln: get Nb-MA solution 10.856g at 700 ℃ of calcining 2h, weighing obtains the solution measured concentration and is: 0.01566gNb 2O 5/ g solution, X-ray diffraction is the result show, the powder that calcining obtains is Nb 2O 5Single-phase (Fig. 1).
3. according to equation:
LiOHH 2O+0.05MgO+0.49Nb 2O 5→ LiNb 0.98Mg 0.05O 3+ 1.5H 2The data that O calculates according to thermogravimetric add 0.131g LiOHH in Nb-MA solution 2O, 0.006gMgO stir and cause dissolving fully in solution.
By spray drying device to the solution granulation, be met certain particle diameter requirement particle.
5. carrying out the powder that sintering obtains at 600 ℃ is MgO (5mol%) doped polycrystalline lithium niobate material.X-ray diffraction is the result show, the powder that obtains is single-phase (as shown in Figure 2).
Synthesizing of embodiment 2:MgO (5mol%) doping near-stoichiometric ratio lithium niobate polycrystal
1. from the compound N b (OH) of niobium 53.776g obtain active stronger Nb with concentrated hydrochloric acid 18ml heating for dissolving 2O 5NH 2O adds citric acid (C 6H 8O 7, citric acid) and 1.117g is in ammoniacal liquor (30%) adjusting pH value 8, and filtration can obtain clear Nb-CA solution.
2. the Nb-CA solution 9.361g that takes a morsel does thermogravimetric analysis and calculates: 0.01517gNb 2O 5/ g solution, X-ray diffraction is the result show, the powder that obtains is Nb 2O 5Single-phase.
3. according to equation:
LiOHH 2O+0.05MgO+0.49Nb 2O 5→ LiNb 0.98Mg 0.05O 3+ 1.5H 2The data that O calculates according to thermogravimetric add 0.478g LiOHH in Nb-CA solution 2O, 0.047gMgO stir and cause dissolving fully in solution.
By spray drying device to the solution granulation, be met certain particle diameter requirement particle.Carrying out the powder that sintering 5h obtains at 600 ℃ is MgO (5mol%) doped polycrystalline lithium niobate material.X-ray diffraction is the result show, the powder that obtains is single-phase.
Synthesizing of embodiment 3:MgO (5mol%) doping near-stoichiometric ratio lithium niobate polycrystal
1. the muriate NbCl of niobium 5Obtained active stronger Nb in 12 hours 2.994g be dissolved in the stirring of 25ml water 2O 5NH 2O and DL-oxysuccinic acid (C 4H 6O 5, DL-MA) 3.674g regulates pH=7 at ammoniacal liquor (30%), and filtration can obtain clear Nb-MA solution.
2. the Nb-MA solution 12.245g that takes a morsel does thermogravimetric analysis and calculates: 0.0236gNb 2O 5/ g solution, X-ray diffraction is the result show, the powder that obtains is Nb 2O 5Single-phase.
3. according to equation:
LiOHH 2O+0.05MgO+0.49Nb 2O 5→ LiNb 0.98Mg 0.05O 3+ 1.5H 2O adds 0.384g LiOHH according to the thermogravimetric data calculated in Nb-MA solution 2O, 0.018gMgO stir and cause dissolving fully in solution.
By spray drying device to the solution granulation;
5. carrying out sintering 5h at 600 ℃, to obtain powder be MgO (5mol%) doped polycrystalline lithium niobate material.X-ray diffraction is the result show, the powder that obtains is single-phase.
Synthesizing of embodiment 4:MgO (5mol%) doping near-stoichiometric ratio lithium niobate polycrystal
1. from the compound N b (OH) of niobium 52.460g obtain active stronger Nb with concentrated hydrochloric acid 10ml heating for dissolving 2O 5NH 2O adds DL-oxysuccinic acid (C 4H 6O 5, DL-MA) 2.674g regulates pH=7 at ammoniacal liquor (30%), and filtration can obtain clear Nb-MA solution.
2. the Nb-MA solution 10.856g that takes a morsel does thermogravimetric analysis and calculates: 0.01566gNb 2O 5/ g solution, X-ray diffraction is the result show, the powder that obtains is Nb 2O 5Single-phase.
3. according to equation:
Li ++ 0.05MgO+0.49Nb 2O 5→ LiNb 0.98Mg 0.05O 3+ 1.5H 2The data that O calculates according to thermogravimetric add 0.006gMgO in Nb-MA solution, be stirred to dissolving fully in solution.
4. with 0.115gLi 2CO 3In dilute hydrochloric acid, join Mg after the dissolving 2+, in the Nb-MA solution, use ammoniacal liquor (30%) to regulate pH=7 at last again.
By spray drying device to the solution granulation, be met certain particle diameter requirement particle.Carrying out the powder that sintering obtains at 600 ℃ is MgO (5at) doped polycrystalline lithium niobate material.X-ray diffraction is the result show, the powder that obtains is single-phase.
Synthesizing of embodiment 5:ZnO (5mol%) doping near-stoichiometric ratio lithium niobate polycrystal
1. from the compound N b (OH) of niobium 52.460g obtain active stronger Nb with concentrated hydrochloric acid 10ml heating for dissolving 2O 5NH 2O adds DL-oxysuccinic acid (C 4H 6O 5, DL-MA) 2.674g regulates pH=8 at ammoniacal liquor (30%), and filtration can obtain clear Nb-MA solution.
2. the Nb-MA solution 10.856g that takes a morsel does thermogravimetric analysis and calculates: 0.01566gNb 2O 5/ g solution, X-ray diffraction is the result show, the powder that obtains is Nb 2O 5Single-phase.
3. according to equation:
LiOHH 2O+0.05ZnO+0.49Nb 2O 5→ LiNb 0.98Zn 0.05O 3+ 1.5H 2The data that O calculates according to thermogravimetric add 0.131g LiOHH in Nb-MA solution 2O, 0.013gZnO stir and cause dissolving fully in solution.
By spray drying device to the solution granulation, be met certain particle diameter requirement particle.Carrying out the powder that sintering 5h obtains at 600 ℃ is ZnO (5mol%) doped polycrystalline lithium niobate material.X-ray diffraction is the result show, the powder that obtains is single-phase.
Synthesizing of embodiment 6:ZnO (5mol%) doping near-stoichiometric ratio lithium niobate polycrystal
1. from the compound N b (OH) of niobium 52.460g obtain active stronger Nb with concentrated hydrochloric acid 12ml heating for dissolving 2O 5NH 2O adds DL-oxysuccinic acid (C 4H 6O 5, DL-MA) 2.674g regulates pH=7 at ammoniacal liquor (30%), and filtration can obtain clear Nb-MA solution.
2. the Nb-MA solution 10.856g that takes a morsel does thermogravimetric analysis and calculates: 0.01566gNb 2O 5/ g solution, X-ray diffraction is the result show, the powder that obtains is Nb 2O 5Single-phase.
3. according to equation:
Li ++ 0.05ZnO+0.49Nb 2O 5→ LiNb 0.98Zn 0.05O 3+ 1.5H 2Data 0.012gZnO in Nb-MA solution that O calculates according to thermogravimetric stirs and causes dissolving fully in solution.
4. with 0.115gLi 2CO 3In dilute hydrochloric acid, join Zn after the dissolving 2+, in the Nb-MA solution, use ammoniacal liquor (30%) to regulate pH=7 at last again.
By spray drying device to the solution granulation, be met certain particle diameter requirement particle.Carrying out the powder that sintering 5h obtains at 600 ℃ is ZnO (5mol%) doped polycrystalline lithium niobate material.X-ray diffraction is the result show, the powder that obtains is single-phase.
Synthesizing of embodiment 7:MgO (5mol%) doping near-stoichiometric ratio lithium niobate polycrystal
1. the muriate NbCl of niobium 52.994g water-soluble stirring obtained active stronger Nb in 12 hours 2O 5NH 2O and DL-oxysuccinic acid (C 4H 6O 5, DL-MA) 3.674g regulates pH=7 at ammoniacal liquor (30%), and filtration can obtain clear Nb-MA solution.
2. the Nb-MA solution 12.245g that takes a morsel does thermogravimetric analysis and calculates: 0.0236gNb 2O 5/ g solution, X-ray diffraction is the result show, the powder that obtains is Nb 2O 5Single-phase.
3. according to equation:
Li ++ 0.05MgO+0.49Nb 2O 5→ LiNb 0.98Mg 0.05O 3+ 1.5H 2O adds 0.018gMgO according to the thermogravimetric data calculated in Nb-MA solution, stir to cause dissolving fully in solution.
4. with 0.679g Li 2CO 3In dilute hydrochloric acid, join Mg after the dissolving 2+, in the Nb-MA solution, use ammoniacal liquor (30%) to regulate pH=7 at last again.
By spray drying device to having the solution granulation, carrying out sintering 5h at 600 ℃, to obtain powder be MgO (5mol%) doped polycrystalline lithium niobate material.X-ray diffraction is the result show, the powder that obtains is single-phase.
Embodiment 8: as described in embodiment 2, that different is the adulterated ZnO of being.
Embodiment 9: as described in embodiment 5, different is that organic solvent is a citric acid.
Embodiment 10: as described in embodiment 6, different is that organic solvent is a citric acid.

Claims (1)

1, the synthetic method of the uniform spherical doped polycrystalline lithium niobate material of a kind of composition, step is as follows:
(1) from the compound N b (OH) of niobium 52.460g obtain active stronger Nb with 36%m/m concentrated hydrochloric acid 10ml heating for dissolving 2O 5NH 2O adds DL-oxysuccinic acid 2.674g and regulates pH=8 with 30%v/v ammoniacal liquor, and filtration can obtain clear Nb-malic acid solution;
(2) get Nb-malic acid solution 10.856g and be thermogravimetric analysis calculating: 0.01566gNb 2O 5/ g solution, X-ray diffraction is the result show, the powder that obtains is Nb 2O 5Single-phase;
(3) according to equation:
LiOH·H 2O+0.05ZnO+0.49Nb 2O 5→LiNb 0.98Zn 0.05O 3+1.5H 2O
The data of calculating according to thermogravimetric add 0.131g LiOHH in the Nb-malic acid solution 2O, 0.013gZnO are stirred to dissolving fully in solution;
(4) by spray drying device to the solution granulation, be met certain particle diameter requirement particle; Carrying out the powder that sintering 5h obtains at 600 ℃ is ZnO doping polycrystalline lithium niobate material.
CNB2007100156753A 2007-06-08 2007-06-08 The synthetic method of the uniform spherical doped polycrystalline lithium niobate material of composition Expired - Fee Related CN100564256C (en)

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CN101319391B (en) * 2008-06-06 2010-11-03 中电科技德清华莹电子有限公司 Synthesis of constituent-homogeneous spherical lithium tantalite doping polycrystal raw material
CN103922405B (en) * 2014-04-18 2015-08-12 山东大学 A kind of mass synthetic method of even mg-doped lithium niobate polycrystal
CN104310479A (en) * 2014-10-16 2015-01-28 河北工业大学 Silver-doped lithium niobate nano polycrystalline powder and preparation method thereof
CN107151142B (en) * 2017-05-26 2020-06-16 中电科技德清华莹电子有限公司 Method for synthesizing polycrystalline material with high-melting-point doping elements
CN109056076A (en) * 2018-07-03 2018-12-21 江南石墨烯研究院 A kind of preparation method of doped lithium columbate presoma and doped polycrystalline lithium niobate material

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