CN102443880A - Preparation method for europium-doped yttrium oxysulfide red luminous nano fiber - Google Patents
Preparation method for europium-doped yttrium oxysulfide red luminous nano fiber Download PDFInfo
- Publication number
- CN102443880A CN102443880A CN201110251481XA CN201110251481A CN102443880A CN 102443880 A CN102443880 A CN 102443880A CN 201110251481X A CN201110251481X A CN 201110251481XA CN 201110251481 A CN201110251481 A CN 201110251481A CN 102443880 A CN102443880 A CN 102443880A
- Authority
- CN
- China
- Prior art keywords
- nanofiber
- europium
- preparation
- nano
- nano fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Luminescent Compositions (AREA)
- Inorganic Fibers (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The invention relates to a preparation method for a europium-doped yttrium oxysulfide red luminous nano fiber, which belongs to the technical field of preparation of nano materials. In the prior art, europium-doped yttrium oxysulfide nanoparticles, nanotubes, nano wires, nano bars, nano flower and polyhedron nano crystalline are prepared. In the invention, a method for combining a static spinning technology with a sulfurization technology is adopted, so that a Y2O2S:3 percent Eu<3+> nano fiber is prepared. The method comprises the following steps of: (1) preparing a Y2O3:3 percent Eu<3+> nano fiber: preparing a PVP/[Y(NO3)<3+>Eu(NO3)3] compound nano fiber by adopting the static spinning technology, and performing thermal treatment to obtain the Y2O3:3 percent Eu<3+> nano fiber; and (2) preparing a Y2O2S:3 percent Eu<3+> nano fiber. The Y2O3:3 percent Eu<3+> nano fiber is sulfurized with sulfur by adopting a double-crucible method, so that a pure-phase Y2O3:3 percent Eu<3+> nano fiber with a good crystal form, the diameter of 137-180 nanometers and the length of more than 100 mum is obtained. The preparation method is easy to operate, and can be applied to batch production. The europium-doped yttrium oxysulfide nano fiber is a novel important red nano fluorescent material, and has wide application prospect.
Description
Technical field
The present invention relates to the nano material preparation technical field, relate to a kind of preparation method who mixes europium yttrium oxysulfide emitting red light nanofiber 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.
Yttrium oxysulfide Y
2O
2S has that chemical stability is good, water insoluble, fusing point is high, non-oxidizability is strong and advantage such as efficiency of light absorption and energy transfer efficiency be high, nontoxic, becomes the important matrix of rare-earth ion activated luminescent material.Europium ion-doped yttrium oxysulfide Y
2O
2S:Eu
3+It is the red illuminating material of one type of important function admirable, extensive use.Y
2O
2S:Eu
3+The research of nano material has caused showing great attention to of people.Adopt hydro-thermal and solvent-thermal method, solid reaction process, firing method, microwave method etc., prepared Y
2O
2S:Eu
3+Nano particle, nanotube, nano wire, nanometer rods, nanometer is colored, polyhedron is nanocrystalline.Y
2O
2S:Eu
3+Nanofiber is a kind of important novel red nano luminescent material, will obtain important application in fields such as luminous and demonstration, false proof, biomarker, nano-devices, has broad application prospects.At present, do not see that Y is arranged
2O
2S:Eu
3+The relevant 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, application number: 200810050959.0).Electrospinning process can prepare big L/D ratio micrometer fibers or nanofiber continuously.At present, do not see have the electrostatic spinning technique of employing to prepare Y
2O
2S:Eu
3+The relevant report of 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 europium oxide Eu
2O
3Be raw material,, obtain Y (NO with evaporating behind the dilute nitric acid dissolution
3)
3And Eu (NO
3)
3Mixed crystal adds solvent N, and 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/ [Y (NO
3)
3+ Eu (NO
3)
3] original nanofiber, it is heat-treated in air, obtain Y
2O
3: Eu
3+Nanofiber adopts double crucible method, is that vulcanizing agent vulcanizes with sulphur, has prepared the Y of the pure phase of novel structure
2O
2S:Eu
3+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 owing to the demand to 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 and rare earth fluoride/rare earth oxyfluoride composite nano fibre.Prior art employing hydro-thermal and solvent-thermal method, solid reaction process, firing method, microwave method etc. have prepared Y
2O
2S:Eu
3+Nano particle, nanotube, nano wire, nanometer rods, nanometer is colored, polyhedron is nanocrystalline.For a kind of novel red luminous nano fibre material is provided in the nanofiber field, we combine electrostatic spinning technique with sulfurization technology, invented Y
2O
2S:Eu
3+The preparation method of 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/ [Y (NO
3)
3+ Eu (NO
3)
3] original nanofiber, it is heat-treated in air, obtain Y
2O
3: Eu
3+Nanofiber adopts double crucible method, is that vulcanizing agent vulcanizes with sulphur, has prepared the Y of the pure phase of novel structure
2O
2S:Eu
3+Nanofiber.In the present invention, the mole percent of the europium ion of doping is 3%, is labeled as Y
2O
2S:3%Eu
3+, i.e. that the present invention is prepared is Y
2O
2S:3%Eu
3+Nanofiber.The steps include:
(1) preparation Y
2O
3: 3%Eu
3+Nanofiber
That use in yttrium source and europium source is yittrium oxide Y
2O
3With europium oxide Eu
2O
3, high polymer templates adopts polyvinylpyrrolidone PVP, and molecular weight is 90000, adopts N, and dinethylformamide DMF is a solvent.Take by weighing a certain amount of yittrium oxide and europium oxide, both mol ratios are 97: 3, and promptly the mole percent of europium ion is 3%, with evaporating behind the dilute nitric acid dissolution, obtain Y (NO
3)
3And Eu (NO
3)
3Mixed crystal adds an amount of DMF solvent, takes by weighing a certain amount of PVP again and joins in the above-mentioned solution, stirs 4h in the room temperature lower magnetic force, and leaves standstill 2h, promptly forms spinning solution.The mass percent of this each part of spinning solution is: rare earth nitrades content 9%, PVP content 9%, solvent DMF content 82%.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 13kV, solidifies apart from 16cm; 18～25 ℃ of room temperatures, relative humidity is 60%～80%, obtains PVP/ [Y (NO
3)
3+ Eu (NO
3)
3] composite nano fiber.With described PVP/ [Y (NO
3)
3+ Eu (NO
3)
3] composite nano fiber 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 Y
2O
3: 3%Eu
3+Nanofiber.
(2) preparation Y
2O
2S:3%Eu
3+Nanofiber
Sulfuration reagent uses sulphur, adopts double crucible method, and sulphur is put into monkey, covers carbon dust above, with described Y
2O
3: 3%Eu
3+Nanofiber is placed on above the carbon dust, and monkey is put into bigger crucible, between interior outer crucible, adds excessive sulphur; Add that on outer crucible the crucible lid puts into tube furnace, when room temperature, feed argon gas 40min, discharge the air in the boiler tube; With the heating rate to 800 of 5 ℃/min ℃, insulation 4h reduces to 200 ℃ with the rate of temperature fall of 5 ℃/min again; Naturally cool to room temperature afterwards, obtain Y
2O
2S:3%Eu
3+Nanofiber, diameter are 137～180nm, and length is greater than 100 μ m.
At the Y described in the said process
2O
2S:3%Eu
3+Nanofiber has good crystal formation, and diameter is 137～180 μ m, and length has realized goal of the invention greater than 100 μ m.
Description of drawings
Fig. 1 is Y
2O
2S:3%Eu
3+The XRD spectra of nanofiber;
Fig. 2 is Y
2O
2S:3%Eu
3+The SEM photo of nanofiber, this figure double as Figure of abstract;
Fig. 3 is Y
2O
2S:3%Eu
3+The EDS spectrogram of nanofiber;
Fig. 4 is Y
2O
2S:3%Eu
3+The exciting light spectrogram of nanofiber;
Fig. 5 is Y
2O
2S:3%Eu
3+The emission spectrum figure of nanofiber.
The specific embodiment
The yittrium oxide Y that the present invention selected for use
2O
3With europium oxide Eu
2O
3Purity be 99.99%, polyvinylpyrrolidone PVP, molecular weight 90000, N, dinethylformamide DMF, sulphur, carbon dust and nitric acid are 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 yittrium oxide and europium oxide, both mol ratios are 97: 3, and promptly the mole percent of europium ion is 3%, with evaporating behind the dilute nitric acid dissolution, obtain Y (NO
3)
3And Eu (NO
3)
3Mixed crystal adds an amount of DMF solvent, takes by weighing a certain amount of PVP again and joins in the above-mentioned solution, stirs 4h in the room temperature lower magnetic force, and leaves standstill 2h, promptly forms spinning solution.The mass percent of this each part of spinning solution is: rare earth nitrades content 9%, PVP content 9%, solvent DMF content 82%.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 13kV, solidifies apart from 16cm; 18～25 ℃ of room temperatures, relative humidity is 60%～80%, obtains PVP/ [Y (NO
3)
3+ Eu (NO
3)
3] composite nano fiber.With described PVP/ [Y (NO
3)
3+ Eu (NO
3)
3] composite nano fiber 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 Y
2O
3: 3%Eu
3+Nanofiber.Sulfuration reagent uses sulphur, adopts double crucible method, and sulphur is put into monkey, covers carbon dust above, with described Y
2O
3: 3%Eu
3+Nanofiber is placed on above the carbon dust, and monkey is put into bigger crucible, between interior outer crucible, adds excessive sulphur; Add that on outer crucible the crucible lid puts into tube furnace, when room temperature, feed argon gas 40min, discharge the air in the boiler tube; With the heating rate to 800 of 5 ℃/min ℃, insulation 4h reduces to 200 ℃ with the rate of temperature fall of 5 ℃/min again; Naturally cool to room temperature afterwards, obtain Y
2O
2S:3%Eu
3+Nanofiber.Described Y
2O
2S:3%Eu
3+Nanofiber has good crystallinity, the d value of its diffraction maximum and relative intensity and Y
2O
2The listed d value of the PDF standard card (24-1424) of S is consistent with relative intensity, belongs to hexagonal crystal system, sees shown in Figure 1.Described Y
2O
2S:3%Eu
3+The diameter of nanofiber is 137～180nm, and length is seen shown in Figure 2 greater than 100 μ m.Y
2O
2S:3%Eu
3+Nanofiber is formed (the Au conductive layer of surface plating when Au comes from the SEM sample preparation) by Y, O, S and Eu element, sees shown in Figure 3.When the monitoring wavelength is 628nm, Y
2O
2S:3%Eu
3+The excitation spectrum highest peak of nanofiber is positioned at the 325nm place, belongs to S
2--Eu
3+Between electric charge migration band, the excitation peak that is positioned at the 258nm place belongs to O
2--Eu
3+Between electric charge migration band, see shown in Figure 4.Under the ultraviolet excitation of 325nm, Y
2O
2S:3%Eu
3+Nanofiber is launched the bright red that main peak is positioned at 628nm, and it is corresponding to Eu
3+Ion
5D
0→
7F
2Transition belongs to Eu
3+Force electric dipole transition, see 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 (5)
1. preparation method who mixes europium yttrium oxysulfide emitting red light nanofiber; It is characterized in that the method that adopts electrostatic spinning technique to combine with sulfurization technology uses polyvinylpyrrolidone PVP to be high polymer templates; Adopt N; Dinethylformamide DMF is a solvent, and sulfuration reagent uses sulphur, and the preparation product is europium ion-doped yttrium oxysulfide Y
2O
2S:3%Eu
3+Nanofiber the steps include:
(1) preparation Y
2O
3: 3%Eu
3+Nanofiber
Take by weighing a certain amount of yittrium oxide and europium oxide, both mol ratios are 97: 3, and promptly the mole percent of europium ion is 3%, with evaporating behind the dilute nitric acid dissolution, obtain Y (NO
3)
3And Eu (NO
3)
3Mixed crystal adds an amount of DMF solvent, takes by weighing a certain amount of PVP again and joins in the above-mentioned solution, stirs 4h in the room temperature lower magnetic force; And leave standstill 2h, and promptly forming spinning solution, the mass percent of this each part of spinning solution is: rare earth nitrades content 9%, PVP content 9%; Solvent DMF content 82% adds the spinning solution for preparing in the liquid storage pipe of device for spinning, carries 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 13kV, solidifies apart from 16cm; 18～25 ℃ of room temperatures, relative humidity is 60%～80%, obtains PVP/ [Y (NO
3)
3+ Eu (NO
3)
3] composite nano fiber, with described PVP/ [Y (NO
3)
3+ Eu (NO
3)
3] composite nano fiber 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 Y
2O
3: 3%Eu
3+Nanofiber;
(2) preparation Y
2O
2S:3%Eu
3+Nanofiber
Sulfuration reagent uses sulphur, adopts double crucible method, and sulphur is put into monkey, covers carbon dust above, with described Y
2O
3: 3%Eu
3+Nanofiber is placed on above the carbon dust, and monkey is put into bigger crucible, between interior outer crucible, adds excessive sulphur; Add that on outer crucible the crucible lid puts into tube furnace, when room temperature, feed argon gas 40min, discharge the air in the boiler tube; With the heating rate to 800 of 5 ℃/min ℃, insulation 4h reduces to 200 ℃ with the rate of temperature fall of 5 ℃/min again; Naturally cool to room temperature afterwards, obtain Y
2O
2S:3%Eu
3+Nanofiber, diameter are 137～180nm, and length is greater than 100 μ m.
2. a kind of preparation method who mixes europium yttrium oxysulfide emitting red light nanofiber according to claim 1 is characterized in that, that use in yttrium source and europium source is yittrium oxide Y
2O
3With europium oxide Eu
2O
3
3. a kind of preparation method who mixes europium yttrium oxysulfide emitting red light nanofiber according to claim 1 is characterized in that high polymer templates is the polyvinylpyrrolidone of molecular weight Mr=90000.
4. a kind of preparation method who mixes europium yttrium oxysulfide emitting red light nanofiber according to claim 1 is characterized in that, sulfuration reagent uses sulphur.
5. a kind of preparation method who mixes europium yttrium oxysulfide emitting red light nanofiber according to claim 1 is characterized in that the Eu of doping
3+Mole percent is 3%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110251481XA CN102443880A (en) | 2011-08-30 | 2011-08-30 | Preparation method for europium-doped yttrium oxysulfide red luminous nano fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110251481XA CN102443880A (en) | 2011-08-30 | 2011-08-30 | Preparation method for europium-doped yttrium oxysulfide red luminous nano fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102443880A true CN102443880A (en) | 2012-05-09 |
Family
ID=46006801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110251481XA Pending CN102443880A (en) | 2011-08-30 | 2011-08-30 | Preparation method for europium-doped yttrium oxysulfide red luminous nano fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102443880A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102817109A (en) * | 2012-08-10 | 2012-12-12 | 长春理工大学 | Preparation method for europium doped yttrium disilicate red luminescence nano-belts |
| CN103774283A (en) * | 2012-10-23 | 2014-05-07 | 中国科学院上海硅酸盐研究所 | Cerium doped silicate lutetium scintillating fiber and electrostatic spinning synthetic method thereof |
| CN103774282A (en) * | 2012-10-23 | 2014-05-07 | 中国科学院上海硅酸盐研究所 | Ce-doped lutetium pyrosilicate scintillating fiber, and electrostatic spinning synthetic method thereof |
| CN104562295A (en) * | 2014-12-29 | 2015-04-29 | 长春理工大学 | Erbium-doped yttrium oxysulfide up-conversion luminescent hollow nanofibers and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640984A (en) * | 2004-12-17 | 2005-07-20 | 中国科学院上海硅酸盐研究所 | Fluorescent powder for transmitting green fluorescence and its preparing method |
| CN102031591A (en) * | 2010-11-19 | 2011-04-27 | 长春理工大学 | Europium-doped Y7O6F9 nano fiber and preparation method thereof |
-
2011
- 2011-08-30 CN CN201110251481XA patent/CN102443880A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640984A (en) * | 2004-12-17 | 2005-07-20 | 中国科学院上海硅酸盐研究所 | Fluorescent powder for transmitting green fluorescence and its preparing method |
| CN102031591A (en) * | 2010-11-19 | 2011-04-27 | 长春理工大学 | Europium-doped Y7O6F9 nano fiber and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 李向果等: "黄色到红色长余辉材料Y2O2S的制备和光谱性能研究", 《韶关学院学报》 * |
| 艾鹏飞等: "纳米晶Y2O2S：Eu3+,Mg2+,Ti4+长余辉发光材料的制备", 《功能材料》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102817109A (en) * | 2012-08-10 | 2012-12-12 | 长春理工大学 | Preparation method for europium doped yttrium disilicate red luminescence nano-belts |
| CN102817109B (en) * | 2012-08-10 | 2014-07-02 | 长春理工大学 | Preparation method for europium doped yttrium disilicate red luminescence nano-belts |
| CN103774283A (en) * | 2012-10-23 | 2014-05-07 | 中国科学院上海硅酸盐研究所 | Cerium doped silicate lutetium scintillating fiber and electrostatic spinning synthetic method thereof |
| CN103774282A (en) * | 2012-10-23 | 2014-05-07 | 中国科学院上海硅酸盐研究所 | Ce-doped lutetium pyrosilicate scintillating fiber, and electrostatic spinning synthetic method thereof |
| CN103774282B (en) * | 2012-10-23 | 2016-01-06 | 中国科学院上海硅酸盐研究所 | One mixes cerium lutetium pyrosilicate scintillating fiber and electrostatic spinning synthetic method thereof |
| CN103774283B (en) * | 2012-10-23 | 2016-04-13 | 中国科学院上海硅酸盐研究所 | One mixes cerium silicic acid lutetium scintillating fiber and electrostatic spinning synthetic method thereof |
| CN104562295A (en) * | 2014-12-29 | 2015-04-29 | 长春理工大学 | Erbium-doped yttrium oxysulfide up-conversion luminescent hollow nanofibers and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102041583B (en) | Method for preparing europium and fluorine-doped yttrium oxide nanofibres | |
| CN102031586B (en) | Method for preparing europium-doped yttrium fluoride nano fiber/polymer composite nano fiber | |
| CN101786596B (en) | Polycrystalline nano-fiber with europium ion doped with lanthanum aluminate and preparation method thereof | |
| CN102031591B (en) | Europium-doped Y7O6F9 nano fiber and preparation method thereof | |
| CN102965762B (en) | Method for preparing Er-Yb co-blended yttrium fluoride up-conversion luminescence hollow nanofibers | |
| CN102392322A (en) | Method for preparing europium-doped sulfur oxide gadolinium light-emitting nanometer fiber | |
| CN102660800B (en) | Method for preparing erbium and ytterbium co-doped sodium yttrium tetrafluoride upconversion luminescent nanofibers | |
| CN102392319B (en) | Preparation method of europium-doped LaOBr nanofiber | |
| CN102443880A (en) | Preparation method for europium-doped yttrium oxysulfide red luminous nano fiber | |
| CN102817114B (en) | Method for preparing europium-doped octafluoro yttrium barium red luminescent nano-fiber | |
| CN102817113B (en) | Preparation method of terbium-doped octafluoro yttrium barium green luminescent nano-fiber | |
| CN102443881B (en) | Preparation method for terbium-doped yttrium oxysulfide fluorescent nano-fibers | |
| CN102605465A (en) | Method for preparing europium-doped LaAlO3 red luminescence hollow nanometer fiber | |
| CN102277658B (en) | Method for preparing yttrium sulfide nano-fibers | |
| CN102817094A (en) | Method for preparing europium doped yttrium disilicate red luminescence nano-fibers | |
| CN102618966A (en) | Method for preparing europium-doped sodium tetrafluoro gadolinium red luminescent nanofiber | |
| CN102605471B (en) | Method for preparing Tb (terbium)-doped sodium yttrium tetrafluoride green luminescent nanometer fiber | |
| CN104562295A (en) | Erbium-doped yttrium oxysulfide up-conversion luminescent hollow nanofibers and preparation method thereof | |
| CN102817108B (en) | Preparation method for terbium doped yttrium trifluoride green luminescence hollow nano-fibers | |
| CN102605469A (en) | Method for preparing Eu (europium)-doped Y4Al2O9 red luminescent nano fiber | |
| CN102392320B (en) | Method for preparing europium-doped LaOBr nanoribbon | |
| CN102392323A (en) | Preparation method of europium ion-doped yttrium oxide sulfide nanometer belt | |
| CN102660804B (en) | Method for preparing terbium doped yttrium lithium tetrafluoride nano-fiber | |
| CN102943320A (en) | Erbium doped yttrium trifluoride upconversion luminescence hollow nanometer fiber preparation method | |
| CN102943321B (en) | Europium doped yttrium trifluoride upconversion luminescence hollow nanometer fiber preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120509 |