CN102817113A - Preparation method of terbium-doped octafluoro yttrium barium green luminescent nano-fiber - Google Patents
Preparation method of terbium-doped octafluoro yttrium barium green luminescent nano-fiber Download PDFInfo
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- CN102817113A CN102817113A CN201210283286XA CN201210283286A CN102817113A CN 102817113 A CN102817113 A CN 102817113A CN 201210283286X A CN201210283286X A CN 201210283286XA CN 201210283286 A CN201210283286 A CN 201210283286A CN 102817113 A CN102817113 A CN 102817113A
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Abstract
The invention relates to a preparation method of terbium-doped octafluoro yttrium barium green luminescent nano-fiber, and belongs to the technical field of nano-grade material preparation. The method comprises four steps that: (1) a spinning liquid is prepared; (2) PVP/[Ba(NO3)2+Y(NO3)3+Tb(NO3)3] composite fiber is prepared with an electro-spinning technology; (3) mixed oxide nano-fiber is prepared, wherein the composite fiber is subjected to a heat treatment, such that the mixed oxide nano-fiber is prepared; and (4) BaY2F8:5% Tb<3+> green luminescent nano-fiber is prepared, wherein a double-crucible method is adopted, and the mixed oxide nano-fiber is subjected to a fluorination treatment by using ammonium bifluoride, such that the BaY2F8:5% Tb<3+> green luminescent nano-fiber is prepared. The nano-fiber has good crystallinity, a diameter of 113.9nm (plus or minus 8.7nm), and a length greater than 50mum. The method provided by the invention is simple and feasible, and can be used in batch productions. Therefore, the method has good application prospect.
Description
Technical field
The present invention relates to the nano material preparation research field, relate to the preparation method who mixes terbium octafluoro yttrium baryta green look luminous nano fibre specifically.
Background technology
Nanofiber is meant the filamentary material that on the three dimensions yardstick of material, has bidimensional to be in nanoscale, and radial dimension is a nanometer scale usually, and length is then bigger.Because the radial dimension of nanofiber is little of nanometer scale; Demonstrate series of characteristics; The most outstanding is that specific area is big; Thereby its surface energy increases with active, and then produces small-size effect, surface or interfacial effect, quantum size effect, macro quanta tunnel effect etc., and therefore shows the specificity of a series of chemistry, physics (heat, light, sound, electricity, magnetic etc.) aspect.In the prior art, a lot of methods that prepare nanofiber are arranged, the method for for example reeling off raw silk from cocoons, template synthetic method, split-phase method and self-assembly method etc.In addition, also has arc evaporation, laser high temperature inustion, compound pyrolysismethod.These three kinds of methods in fact all are after at high temperature making compound (or simple substance) evaporation, make nanofiber or nanotube through pyrolysis (or directly condensation), from essence, all belong to the compound steam sedimentation.
Rare earth eight fluorides are one of present efficient rare-earth ion doping luminous hosts owing to have abundant 4f energy level and lower phonon ability.Mix terbium octafluoro yttrium barium BaY
2F
8: Tb
3+Be a kind of important green luminescent material, have important application prospects.At present, BaY
2F
8: Tb
3+Powder body material mainly adopts methods such as high temperature solid-state method, hydro-thermal and solvent-thermal method, sol-gel process, microemulsion method, microwave method, firing method, laser ablation method, presoma pyrolysismethod to synthesize, and synthetic product is BaY
2F
8: Tb
3+Micron particles or nano particle.Mix terbium octafluoro yttrium barium BaY
2F
8: Tb
3+Nanofiber is a kind of novel green luminescent material, will obtain important application in fields such as luminous and demonstration, false proof, medical science detection, biomarker, solar cell, chemistry and biology sensor, nano-devices, has broad application prospects.At present, do not see and mix terbium octafluoro yttrium barium BaY
2F
8: Tb
3+The report of nanofiber.
The patent No. is the technical scheme that 1975504 United States Patent (USP) discloses a relevant electrospinning process (electrospinning); This method is a kind of effective ways that prepare continuous, as to have macro length micro nanometer fiber, is at first proposed in 1934 by Formhals.This method mainly is used for preparing high polymer nanometer fiber; It is characterized in that making charged Polymer Solution or melt in electrostatic field, to receive the traction of electrostatic force and spray, invest the receiving screen on opposite, thereby realize wire drawing by nozzle; Then; Solvent evaporation at normal temperatures, perhaps melt is cooled to normal temperature and solidifies, and obtains micro nanometer fiber.Over nearly 10 years, occurred adopting electrospinning process to prepare the technical scheme of inorganic compound such as oxidate nano fiber at the inorfil preparing technical field, described oxide comprises TiO
2, ZrO
2, Y
2O
3, Y
2O
3: RE
3+(RE
3+=Eu
3+, Tb
3+, Er
3+, Yb
3+/ Er
3+), NiO, Co
3O
4, Mn
2O
3, Mn
3O
4, CuO, SiO
2, Al
2O
3, V
2O
5, ZnO, Nb
2O
5, MoO
3, CeO
2, LaMO
3(M=Fe, Cr, Mn, Co, Ni, Al), Y
3Al
5O
12, La
2Zr
2O
7Deng metal oxide and composite oxide of metal.Employing electrostatic spinning techniques such as Wang Jinxian have prepared rare earth fluoride/rare earth oxyfluoride composite nano fibre (Chinese invention patent, grant number: ZL200810050959.0); Employing electrostatic spinning techniques such as Dong Xiangting have prepared mixes europium Y
7O
6F
9Nanofiber (Chinese invention patent, grant number: ZL201010550196.3); Employing electrostatic spinning techniques such as Wang Jinxian have prepared rare earth trifluoride nanofiber (Chinese invention patent, grant number: ZL201010107993.4); Wang Ce etc. adopt electrostatic spinning technique to pass through R (CF
3CO
2)
3/ PVP (R=Eu, Ho) heat-treat, and synthesized ROF (R=Eu, Ho) nanofiber (J.Nanosci.Nanotechnol., 2009,9 (2): 1522-1525) by composite nano fiber.Electrospinning process can prepare big L/D ratio micrometer fibers or nanofiber continuously.Do not see at present to adopt electrostatic spinning technique to combine to prepare and mix terbium octafluoro yttrium barium BaY with fluorination technology
2F
8: Tb
3+The report of green emitting nanofiber.
When utilizing electrostatic spinning technique to prepare nano material, the composition of the kind of raw material, the molecular weight of high polymer templates, spinning solution, spinning process parameter and Technology for Heating Processing all have material impact to the pattern and the size of final products.The present invention adopts electrostatic spinning technique earlier, with yittrium oxide Y
2O
3With terbium oxide Tb
4O
7Be raw material,, obtain yttrium nitrate Y (NO with evaporating behind the nitric acid dissolve
3)
3With terbium nitrate Tb (NO
3)
3Mixed crystal adds barium nitrate Ba (NO
3)
2, solvent N, dinethylformamide DMF and high polymer templates polyvinylpyrrolidone PVP obtain carrying out electrostatic spinning behind the spinning solution, under the experiment condition of the best, prepare PVP/ [Ba (NO
3)
2+ Y (NO
3)
3+ Tb (NO
3)
3] composite fibre, it is heat-treated in air, obtain the mixed oxide nanoparticle fiber, adopt double crucible method, with ammonium acid fluoride NH
4HF
2Fluoridize for fluorization agent, prepared the BaY of the pure phase of novel structure
2F
8: Tb
3+The green emitting nanofiber.
Summary of the invention
Various in background technology prepare in the method for nanofiber, the shortcoming of the method for reeling off raw silk from cocoons be solution viscosity is required too harsh; The shortcoming of template synthetic method is to prepare the continuous fibers that the root root separates; Split-phase method and self-assembly method production efficiency are all lower; And the compound steam sedimentation is because to the demand of high temperature, so process conditions are difficult to control, and the nanofiber major diameter of above-mentioned several method preparation is than little.Use electrostatic spinning technique in the background technology has prepared metal oxide, composite oxide of metal nanofiber, rare earth fluoride/rare earth oxyfluoride composite nano fibre, has mixed europium Y
7O
6F
9Nanofiber, rare earth trifluoride nanofiber and ROF (R=Eu, Ho) nanofiber.Prior art adopts methods such as high temperature solid-state method, hydro-thermal and solvent-thermal method, sol-gel process, microemulsion method, microwave method, firing method, laser ablation method, presoma pyrolysismethod to synthesize BaY
2F
8: Tb
3+Micron particles or nano particle.For a kind of novel green luminous nano fibre material is provided in the nanofiber field, we combine electrostatic spinning technique with fluorination technology, invented BaY
2F
8: Tb
3+The preparation method of green emitting nanofiber.
The present invention is achieved in that and at first prepares the spinning solution with certain viscosity that is used for electrostatic spinning, uses electrostatic spinning technique and carries out electrostatic spinning, under the experiment condition of the best, prepares PVP/ [Ba (NO
3)
2+ Y (NO
3)
3+ Tb (NO
3)
3] composite fibre, it is heat-treated in air, obtained the mixed oxide nanoparticle fiber, adopt double crucible method, with ammonium acid fluoride NH
4HF
2Fluoridize for fluorization agent, prepared the BaY of the pure phase of novel structure
2F
8: Tb
3+The green emitting nanofiber.In the present invention, the mole percent of the terbium ion of doping is 5%, is labeled as BaY
2F
8: 5%Tb
3+, i.e. that the present invention is prepared is BaY
2F
8: 5%Tb
3+The green emitting nanofiber.The steps include:
(1) preparing spinning solution
That use in the barium source is barium nitrate Ba (NO
3)
2, that use in yttrium source and terbium source is yittrium oxide Y
2O
3With terbium oxide Tb
4O
7, high polymer templates adopts polyvinylpyrrolidone PVP, and molecular weight is 90000, adopts N, and dinethylformamide DMF is a solvent, takes by weighing a certain amount of barium nitrate Ba (NO
3)
2, yittrium oxide Y
2O
3With terbium oxide Tb
4O
7, Ba wherein
2+, Y
3+And Tb
3+Mol ratio be 50: 95: 5, promptly the mole percent of terbium ion is 5%, with yittrium oxide Y
2O
3With terbium oxide Tb
4O
7Use nitric acid HNO
3The evaporation of dissolving back obtains Y (NO
3)
3And Tb (NO
3)
3Mixed crystal adds barium nitrate Ba (NO
3)
2, N, dinethylformamide DMF solvent and polyvinylpyrrolidone PVP stir 4h in the room temperature lower magnetic force; And leave standstill 2h, and forming spinning solution, the mass percent of this each part of spinning solution is: nitrate content 9%; PVP content 12%, solvent DMF content 79%;
(2) preparation PVP/ [Ba (NO
3)
2+ Y (NO
3)
3+ Tb (NO
3)
3] composite fibre
The spinning solution for preparing is added in the liquid storage pipe of device for spinning, carry out electrostatic spinning, shower nozzle internal diameter 0.7mm; The angle of adjustment shower nozzle and horizontal plane is 15 °, applies the DC voltage of 15kY, solidifies apart from 16cm; 20~28 ℃ of room temperatures, relative humidity is 45%~75%, obtains PVP/ [Ba (NO
3)
2+ Y (NO
3)
3+ Tb (NO
3)
3] composite fibre;
(3) preparation mixed oxide nanoparticle fiber
With described PVP/ [Ba (NO
3)
2+ Y (NO
3)
3+ Tb (NO
3)
3] composite fibre is put in the temperature programmed control stove and heat-treats, heating rate is 1 ℃/min, at 700 ℃ of constant temperature 8h, the speed with 1 ℃/min is cooled to 200 ℃ again, naturally cools to room temperature with body of heater afterwards, obtains the mixed oxide nanoparticle fiber;
(4) preparation BaY
2F
8: 5%Tb
3+The green emitting nanofiber
Fluorination reagent uses ammonium acid fluoride NH
4HF
2, adopt double crucible method, ammonium acid fluoride is put into monkey; Cover carbon-point above, described mixed oxide nanoparticle fiber is placed on above the carbon-point, monkey is put into bigger crucible; Between interior outer crucible, add an amount of ammonium acid fluoride, add that on outer crucible the crucible lid puts into tube furnace, be warming up to 280 ℃ of insulation 2h with the heating rate of 2 ℃/min; Be warmed up to 700 ℃ of insulation 4h again; Rate of temperature fall with 1 ℃/min is cooled to 200 ℃ at last, naturally cools to room temperature with body of heater afterwards, obtains BaY
2F
8: 5%Tb
3+Green emitting nanofiber, diameter are 113.9 ± 8.7nm, and length is greater than 50 μ m.
At the BaY described in the said process
2F
8: 5%Tb
3+The green emitting nanofiber has good crystallinity, and diameter is 113.9 ± 8.7nm, and length has realized goal of the invention greater than 50 μ m.
Description of drawings
Fig. 1 is BaY
2F
8: 5%Tb
3+The XRD spectra of green emitting nanofiber;
Fig. 2 is BaY
2F
8: 5%Tb
3+The SEM photo of green emitting nanofiber, this figure double as Figure of abstract;
Fig. 3 is BaY
2F
8: 5%Tb
3+The diameter Distribution histogram of green emitting nanofiber;
Fig. 4 is BaY
2F
8: 5%Tb
3+The exciting light spectrogram of green emitting nanofiber;
Fig. 5 is BaY
2F
8: 5%Tb
3+The emission spectrum figure of green emitting nanofiber.
The specific embodiment
The yittrium oxide Y that the present invention selected for use
2O
3With terbium oxide Tb
4O
7Purity be 99.99%, polyvinylpyrrolidone PVP, molecular weight 90000, N, dinethylformamide DMF, carbon-point, barium nitrate Ba (NO
3)
2, ammonium acid fluoride NH
4HF
2With nitric acid HNO
3Be commercially available analysis net product; Used glass apparatus, crucible and equipment are instrument and equipments commonly used in the laboratory.
Embodiment: take by weighing a certain amount of barium nitrate Ba (NO
3)
2, yittrium oxide Y
2O
3With terbium oxide Tb
4O
7, Ba wherein
2+, Y
3+And Tb
3+Mol ratio be 50: 95: 5, promptly the mole percent of terbium ion is 5%, with yittrium oxide Y
2O
3With terbium oxide Tb
4O
7Use nitric acid HNO
3The evaporation of dissolving back obtains Y (NO
3)
3And Tb (NO
3)
3Mixed crystal adds barium nitrate Ba (NO
3)
2, N, dinethylformamide DMF solvent and polyvinylpyrrolidone PVP stir 4h in the room temperature lower magnetic force; And leave standstill 2h, and forming spinning solution, the mass percent of this each part of spinning solution is: nitrate content 9%; PVP content 12%, solvent DMF content 79%; The spinning solution for preparing is added in the liquid storage pipe of device for spinning, carry out electrostatic spinning, shower nozzle internal diameter 0.7mm; The angle of adjustment shower nozzle and horizontal plane is 15 °, applies the DC voltage of 15kV, solidifies apart from 16cm; 20~28 ℃ of room temperatures, relative humidity is 45%~75%, obtains PVP/ [Ba (NO
3)
2+ Y (NO
3)
3+ Tb (NO
3)
3] composite fibre; With described PVP/ [Ba (NO
3)
2+ Y (NO
3)
3+ Tb (NO
3)
3] composite fibre is put in the temperature programmed control stove and heat-treats, heating rate is 1 ℃/min, at 700 ℃ of constant temperature 8h, the speed with 1 ℃/min is cooled to 200 ℃ again, naturally cools to room temperature with body of heater afterwards, obtains the mixed oxide nanoparticle fiber; Fluorination reagent uses ammonium acid fluoride NH
4HF
2, adopt double crucible method, ammonium acid fluoride is put into monkey; Cover carbon-point above, described mixed oxide nanoparticle fiber is placed on above the carbon-point, monkey is put into bigger crucible; Between interior outer crucible, add an amount of ammonium acid fluoride, add that on outer crucible the crucible lid puts into tube furnace, be warming up to 280 ℃ of insulation 2h with the heating rate of 2 ℃/min; Be warmed up to 700 ℃ of insulation 4h again; Rate of temperature fall with 1 ℃/min is cooled to 200 ℃ at last, naturally cools to room temperature with body of heater afterwards, obtains BaY
2F
8: 5%Tb
3+The green emitting nanofiber.Described BaY
2F
8: 5%Tb
3+The green emitting nanofiber has good crystallinity, the d value of its diffraction maximum and relative intensity and BaY
2F
8The listed d value of PDF standard card (45-0246) consistent with relative intensity, belong to monoclinic system, see shown in Figure 1.Described BaY
2F
8: 5%Tb
3+The diameter of green emitting nanofiber is even, is fibrous, and length is seen shown in Figure 2 greater than 50 μ m.With the Shapiro-Wilk method to BaY
2F
8: 5%Tb
3+The diameter of green emitting nanofiber carries out normal distribution-test, under 95% confidence level, and BaY
2F
8: 5%Tb
3+The diameter Distribution of green emitting nanofiber belongs to normal distribution, and diameter is 113.9 ± 8.7nm, sees shown in Figure 3.When the monitoring wavelength is 543nm, BaY
2F
8: 5%Tb
3+The strongest excitation peak of nanofiber is positioned at the 369nm place, corresponding to Tb
3+ 7F
6→
5D
3Transition is seen shown in Figure 4.Under the ultraviolet excitation of 369nm, BaY
2F
8: 5%Tb
3+Nanofiber is launched the bright green glow that main peak is positioned at 543nm, corresponding to Tb
3+Ion
5D
4→
7F
5Transition, as shown in Figure 5.
Certainly; The present invention also can have other various embodiments; Under the situation that does not deviate from spirit of the present invention and essence thereof; Those of ordinary skill in the art work as can make various corresponding changes and distortion according to the present invention, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.
Claims (2)
1. mix the preparation method of terbium octafluoro yttrium baryta green look luminous nano fibre, it is characterized in that, the method that adopts electrostatic spinning technique to combine with fluorination technology; Use polyvinylpyrrolidone PVP to be high polymer templates; Adopt N, dinethylformamide DMF is a solvent, and fluorination reagent uses ammonium acid fluoride NH
4HF
2, the preparation product is terbium ion doping octafluoro yttrium barium BaY
2F
8: 5%Tb
3+The green emitting nanofiber the steps include:
(1) preparing spinning solution
That use in the barium source is barium nitrate Ba (NO
3)
2, that use in yttrium source and terbium source is yittrium oxide Y
2O
3With terbium oxide Tb
4O
7, high polymer templates adopts polyvinylpyrrolidone PVP, adopts N, and dinethylformamide DMF is a solvent, takes by weighing a certain amount of barium nitrate Ba (NO
3)
2, yittrium oxide Y
2O
3With terbium oxide Tb
4O
7, Ba wherein
2+, Y
3+And Tb
3+Mol ratio be 50: 95: 5, promptly the mole percent of terbium ion is 5%, with yittrium oxide Y
2O
3With terbium oxide Tb
4O
7Use nitric acid HNO
3The evaporation of dissolving back obtains Y (NO
3)
3And Tb (NO
3)
3Mixed crystal adds barium nitrate Ba (NO
3)
2, N, dinethylformamide DMF solvent and polyvinylpyrrolidone PVP stir 4h in the room temperature lower magnetic force; And leave standstill 2h, and forming spinning solution, the mass percent of this each part of spinning solution is: nitrate content 9%; PVP content 12%, solvent DMF content 79%;
(2) preparation PVP/ [Ba (NO
3)
2+ Y (NO
3)
3+ Tb (NO
3)
3] composite fibre
The spinning solution for preparing is added in the liquid storage pipe of device for spinning, carry out electrostatic spinning, shower nozzle internal diameter 0.7mm; The angle of adjustment shower nozzle and horizontal plane is 15 °, applies the DC voltage of 15kV, solidifies apart from 16cm; 20~28 ℃ of room temperatures, relative humidity is 45%~75%, obtains PVP/ [Ba (NO
3)
2+ Y (NO
3)
3+ Tb (NO
3)
3] composite fibre;
(3) preparation mixed oxide nanoparticle fiber
With described PVP/ [Ba (NO
3)
2+ Y (NO
3)
3+ Tb (NO
3)
3] composite fibre is put in the temperature programmed control stove and heat-treats, heating rate is 1 ℃/min, at 700 ℃ of constant temperature 8h, the speed with 1 ℃/min is cooled to 200 ℃ again, naturally cools to room temperature with body of heater afterwards, obtains the mixed oxide nanoparticle fiber;
(4) preparation BaY
2F
8: 5%Tb
3+The green emitting nanofiber
Fluorination reagent uses ammonium acid fluoride NH
4HF
2, adopt double crucible method, ammonium acid fluoride is put into monkey; Cover carbon-point above, described mixed oxide nanoparticle fiber is placed on above the carbon-point, monkey is put into bigger crucible; Between interior outer crucible, add an amount of ammonium acid fluoride, add that on outer crucible the crucible lid puts into tube furnace, be warming up to 280 ℃ of insulation 2h with the heating rate of 2 ℃/min; Be warmed up to 700 ℃ of insulation 4h again; Rate of temperature fall with 1 ℃/min is cooled to 200 ℃ at last, naturally cools to room temperature with body of heater afterwards, obtains BaY
2F
8: 5%Tb
3+Green emitting nanofiber, diameter are 113.9 ± 8.7nm, and length is greater than 50 μ m.
2. the preparation method who mixes terbium octafluoro yttrium baryta green look luminous nano fibre according to claim 1 is characterized in that high polymer templates is the polyvinylpyrrolidone of molecular weight Mr=90000.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104059668A (en) * | 2013-03-21 | 2014-09-24 | 海洋王照明科技股份有限公司 | Terbium/ytterbium double-doped alkaline earth sodium yttrium fluoride up-conversion luminescent material, preparation method and organic light-emitting diode |
CN104562183A (en) * | 2014-12-31 | 2015-04-29 | 西南技术物理研究所 | Method for growing large-sized rare-earth-doped barium yttrium fluoride single crystals |
CN106120023A (en) * | 2016-07-04 | 2016-11-16 | 长春理工大学 | A kind of method preparing er-doped yttrium fluoride barium up-conversion luminescence nanofiber |
CN113957566A (en) * | 2021-11-20 | 2022-01-21 | 福州大学 | Solid oxide battery composite nanofiber and preparation method thereof |
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US1975504A (en) * | 1929-12-07 | 1934-10-02 | Richard Schreiber Gastell | Process and apparatus for preparing artificial threads |
CN102060318A (en) * | 2010-11-19 | 2011-05-18 | 长春理工大学 | Terbium (Tb) doped Y7O6F9 nanobelt and preparation method thereof |
CN102061172A (en) * | 2010-11-19 | 2011-05-18 | 长春理工大学 | Europium (Eu) ion doped Y7O6F9 nanobelt and preparation method thereof |
CN102605471A (en) * | 2012-02-24 | 2012-07-25 | 长春理工大学 | Method for preparing Tb (terbium)-doped sodium yttrium tetrafluoride green luminescent nanometer fiber |
-
2012
- 2012-08-10 CN CN201210283286.XA patent/CN102817113B/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1975504A (en) * | 1929-12-07 | 1934-10-02 | Richard Schreiber Gastell | Process and apparatus for preparing artificial threads |
CN102060318A (en) * | 2010-11-19 | 2011-05-18 | 长春理工大学 | Terbium (Tb) doped Y7O6F9 nanobelt and preparation method thereof |
CN102061172A (en) * | 2010-11-19 | 2011-05-18 | 长春理工大学 | Europium (Eu) ion doped Y7O6F9 nanobelt and preparation method thereof |
CN102605471A (en) * | 2012-02-24 | 2012-07-25 | 长春理工大学 | Method for preparing Tb (terbium)-doped sodium yttrium tetrafluoride green luminescent nanometer fiber |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104059668A (en) * | 2013-03-21 | 2014-09-24 | 海洋王照明科技股份有限公司 | Terbium/ytterbium double-doped alkaline earth sodium yttrium fluoride up-conversion luminescent material, preparation method and organic light-emitting diode |
CN104562183A (en) * | 2014-12-31 | 2015-04-29 | 西南技术物理研究所 | Method for growing large-sized rare-earth-doped barium yttrium fluoride single crystals |
CN104562183B (en) * | 2014-12-31 | 2018-01-19 | 西南技术物理研究所 | Large scale rare-earth adulterates yttrium fluoride barium method for monocrystal growth |
CN106120023A (en) * | 2016-07-04 | 2016-11-16 | 长春理工大学 | A kind of method preparing er-doped yttrium fluoride barium up-conversion luminescence nanofiber |
CN106120023B (en) * | 2016-07-04 | 2018-05-22 | 长春理工大学 | A kind of method for preparing er-doped yttrium fluoride barium up-conversion luminescence nanofiber |
CN113957566A (en) * | 2021-11-20 | 2022-01-21 | 福州大学 | Solid oxide battery composite nanofiber and preparation method thereof |
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