CN101294071A - Core-shell structured fluorescence granular material with adjustable luminescence and preparation method thereof - Google Patents
Core-shell structured fluorescence granular material with adjustable luminescence and preparation method thereof Download PDFInfo
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- CN101294071A CN101294071A CNA2008100625820A CN200810062582A CN101294071A CN 101294071 A CN101294071 A CN 101294071A CN A2008100625820 A CNA2008100625820 A CN A2008100625820A CN 200810062582 A CN200810062582 A CN 200810062582A CN 101294071 A CN101294071 A CN 101294071A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000011258 core-shell material Substances 0.000 title claims description 24
- 239000008187 granular material Substances 0.000 title claims description 20
- 238000002796 luminescence method Methods 0.000 title 1
- 239000000463 material Substances 0.000 claims abstract description 53
- 239000002245 particle Substances 0.000 claims abstract description 30
- 235000019832 sodium triphosphate Nutrition 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 32
- 150000002910 rare earth metals Chemical class 0.000 claims description 18
- -1 phosphate anion Chemical class 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000011824 nuclear material Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 101710194948 Protein phosphatase PhpP Proteins 0.000 claims description 5
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012982 microporous membrane Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 230000002459 sustained effect Effects 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- 239000002096 quantum dot Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910003402 CdSe-ZnS Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000000159 protein binding assay Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000002165 resonance energy transfer Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention relates to a Y2O3:Eu-LnPO4 fluorescent particle material of kernel-housing structure with adjustable light emission. The kernel material is selected from a Y2O3:Eu fluorescent material capable of emitting red light, and the housing material is selected from an LnPO4 fluorescent material capable of emitting green light, wherein the kernel has a size within 4 to 8 mum, and the molar ratio of the Y2O3:Eu material to the LnPO4 material is 1:0.4 to 1:2. The preparation method comprises the following steps: adding a rear earth ion mixture solution for preparing the housing material into a sodium tripolyphosphate solution dropwise, adding the Y2O3:Eu micrometer particles as the kernel, growing the LnPO4 housing layer on the kernel of the Y2O3:Eu micrometer particles, cooling, filtering, cleaning, vacuum drying and collecting the product. The preparation process is simple, and the Y2O3:Eu-LnPO4 fluorescent particle material has stable and adjustable light emission.
Description
Technical field
The present invention relates to a kind of rare earth compound fluorescent material, particularly relate to luminous adjustable Y
2O
3: Eu-LnPO
4Core-shell structured fluorescence granular material and preparation method thereof.
Background technology
In fluorescent material, the rare earth compound fluorescent material is of a great variety because of it, excellent performance is extremely paid attention to.And in the rare earth compound fluorescent material, the research of polycomponent rare earth oxide matrix system is occupy dominant position, Martinez-Rubio, M.I.; Ireland, T.G.; Fern, G.R.; Silver, J.; Snowden, M.J., A New Application for Microgels:Novel Method for the Synthesis of Spherical Particlesof the Y2O3: Eu Phosphor Using a Copolymer Microgel of NIPAM and Acrylic Acid, LANGMUIR, 2001,17 (22): 7145-7149, but the color of light that these rare-earth luminescent materials send is often single, Ronda, C.R.; J ü stel T.; Nikol H., Rare earth phosphors:fundamentalsand applications JOURNAL OFALLOYS AND COMPOUNDS, 1998,275-277:669-676, if will obtain compound coloured light, then need two or more rare-earth luminescent material by mixing, the blending ratio difference, the compound coloured light that obtains is just different.For example in by the three primary colours energy-saving fluorescent lamp that extensively is suitable for, the fluorescent material with three kinds of different colours of red, green, blue mixes according to a certain percentage exactly, and the mixed-color light of sending after it is stimulated is a white light.Feldmann, C.; J ü stel, T.; Ronda C.R.; Schmidt, P.J., Inorganic Luminescent Materials:100 Years of Research and Application, ADVANCED FUNCTIONAL MATERIALS, 2003,13:511-516, but when fluorescent material mixing that will be not homochromy, each particle still only can send own original coloured light, so have aberration closely the time.And different practical physical chemical property differences, when being applied to industry, As time goes on, difference can take place and have influence on photochromic homogeneity therefrom in the absorption of variable grain and stability.Prepare luminous material with adjustable the most frequently used to be nucleocapsid structure.The luminous adjustable material of nuclear-hull shape formula of report is mainly two classes at present, and the first kind is as CdS-ZnS, the semiconductor-quantum-point of CdSe-ZnS and so on, Manna, L.; Scher, E.C.; Li, L.S.; Alivisatos, A.P., Epitaxial growth andphotochemical annealing of graded CdS/ZnS shells on colloidal CdSe nanorods, JOURNAL OF THE AMERICAN CHEMICALSOCIETY, 2002,124:7136-7145.Manna, L.; Scher, E.C.; Li, L.S.; Alivisatos, A.P., Epitaxial growth and photochemical annealingof graded CdS/ZnS shells on colloidal CdSe nanorods, JOURNAL OF THEAMERICAN CHEMICAL SOCIETY, 2002,124:7136-7145., its core is the semiconductor substance with high-luminous-efficiency, outer shell mostly is non-luminous sulfide, and shell mainly is luminous quantum efficiency and the photochemical stability in order to further raising stratum nucleare material.This class nucleocapsid structure is the adjustability that easily realizes glow color by the size that changes quantum dot.Second class is by the derivative luminous microballoon of quantum dot.Han et al is embedded in quantum dot in polymer (polystyrene) microballoon, by the quantity of quantum dot and the size of each quantum dot in the control microballoon, has obtained the adjustable luminous microballoon of luminous intensity and emission wavelength; Willard, D.M.; Carillo, L.L.; Jung, J.; Orden A.V., CdSe-ZnS Quantum Dots as Resonance Energy Transfer Donors in a Model Protein-Protein Binding Assay, NANO LETTERS, 2001,1 (9): 469-474., afterwards, Jyongsik Jang et al was inlaid into the pyrene embedding in the polypyrrole, had also obtained the adjustable luminous microballoon of nuclear-shell of emission wavelength.Han, M.; Gao, X.; Su, J.Z.; Nie S., Quantum-dot-tagged microbeads for multiplexed optical coding ofbiomolecules, NATURE BIOTECHNOLOGY, 2001,19:631-635., more than in the two class nucleocapsid structures, shell is non-luminous complementary material, change luminous be by the particle diameter that changes the internal layer luminescent material or quantity what, these material preparation methods are all difficult, are unsuitable for industrialized large-scale production.Jang J.; Oh J.H., Facile fabrication of photochromic dye-conductingpolymer core-shell nanomaterials and their photoluminescence, ADVANCED MATERIALS, 2003,15:977-980., if stratum nucleare and shell all are luminescent materials independently, then by changing the relative proportion between the nuclear-shell, just can be so that one micro materials sends different compound coloured light relatively equably.This method preparation is simple, made material is luminous stablize adjustable, can commercial scale production, for the luminouslighting industry using value is arranged very.
Summary of the invention
The object of the invention proposes a kind of fluorescence granular material of nucleocapsid structure in order to overcome existing luminous material with adjustable preparation method's shortcoming, and preparation is simple, material is luminous stablize adjustable, Y that can commercial scale production
2O
3: Eu-LnPO
4The preparation method of nuclear-shell fluorescent grain.
The fluorescence granular material of nucleocapsid structure provided by the invention, stratum nucleare and shell are independently luminescent material, and inner nuclear material is the Y that glows
2O
3: Eu micron particle, sheating material are the LnPO of green light
4Fluorescent material, LnPO
4=LaPO
4: Ce, Tb; Described kernel size is 4～8 μ m, and the size of core-shell particle is 6～16 μ m; Described inner nuclear material Y
2O
3: the mol ratio of Eu is: 95: 5～91: 9; Described sheating material La: the mol ratio of Ce: Tb is: 0.60: 0.27: 0.13～0.55: 0.30: 0.15; Described (Y
2O
3: Eu): LnPO
4Mol ratio be: 1: 0.4～1: 2.
The preparation method of the fluorescence granular material of nucleocapsid structure provided by the invention dropwise adds the mixed rare earth ionic solution for preparing sheating material in the tripolyphosphate sodium water solution, adds the Y as kernel again
2O
3: the Eu micron particle, under the certain reaction condition, tripoly phosphate sodium STPP progressively after the hydrolysis formed phosphate anion combine with rare earth ion in the solution, with Y
2O
3: the Eu micron particle is that core growth forms LnPO
4Shell; Through cooling, filtration, washing, collect after the vacuum-drying, obtain the fluorescence granular material of nucleocapsid structure.Comprise the steps:
1. preparation rare-earth ion solution: respectively with 0.04～0.30molLa
2O
3, 0.08～0.60mol Tb (NO
3)
36H
2O, 0.08～0.60mol Ce (NO
3)
36H
2O is dissolved in the rare nitric acid of 1L0.01M, is mixed with volumetric molar concentration to be: the rare-earth ion solution of 0.08～0.60M;
2. preparation mixed rare earth ionic solution: from the rare-earth ion solution that the above-mentioned the first step is prepared, press La: Ce: the mol ratio of the material of Tb 0.60: 0.27: 0.13～0.55: 0.30: 0.15, be mixed with mixed rare earth ionic solution, with salt acid for adjusting pH value to 2.5～3.5, the pH value is measured by accurate pH test paper, obtains mixed rare earth ionic solution;
3. preparation sodium tripolyphosphate solution: take by weighing tripoly phosphate sodium STPP, it is soluble in water, successively the pH value of solution value is adjusted to 2.5～3.5 with 6M and 1M hydrochloric acid, be mixed with the sodium tripolyphosphate solution that volumetric molar concentration is 0.04～0.06M;
4. with above-mentioned second mixed rare earth ionic solution that goes on foot, continuing under the condition of stirring, by mixed rare earth ionic solution and sodium tripolyphosphate solution mol ratio be: dropwise added in 1: 1～1: 1.4 in the tripolyphosphate sodium water solution in above-mentioned the 3rd step, rate of addition is 1 droplet/second, stir, obtain preparing the mixing solutions of sheating material;
5. take by weighing the Y that size is 4～8 μ m
2O
3: the Eu micron particle, press inner nuclear material Y
2O
3: Eu and sheating material LnPO
4Mol ratio be to carry out weighing in 1: 0.4～1: 2, insert in the mixing solutions of above-mentioned the 4th step preparation sheating material, when keeping stirring, placed 90 ℃～98 ℃ following sustained reactions 3～5 hours;
6. after reaction finishes, system is cooled to room temperature, goes out precipitation with the filtering with microporous membrane of 0.22 μ m, the gained precipitate with deionized water repeatedly thoroughly after the washing, placed 30 ℃ of vacuum drying ovens dryings 12～24 hours, obtained Y
2O
3: Eu-LnPO
4Nuclear-shell fluorescence granular material.
Fluorescent grain of the present invention is when being subjected to ultraviolet excitation, and stratum nucleare and shell can send different color light.Along with (Y
2O
3: Eu): LnPO
4The reducing of mol ratio numerical value, the mixed-color light medium green colour content that the core-shell structured fluorescence particulate is launched increases gradually, red composition reduces gradually, and by regulating the relative thickness ratio of stratum nucleare and shell, this core-shell particle can send adjustable compound coloured light relatively equably.
The Y of nucleocapsid structure provided by the invention
2O
3: Eu-LnPO
4Fluorescence granular material.Preparation technology is simple, luminously stablizes adjustablely, is suitable for producing in batches, has significant application value for the luminouslighting industry.
Description of drawings
Fig. 1 scanning electron microscope photograph (a) is the Y as kernel
2O
3: the Eu particle; (b) be the Y behind the formation nucleocapsid structure
2O
3: Eu-LnPO
4Fluorescent grain.
Fig. 2 is as the Y of kernel
2O
3: Eu particle and Y
2O
3: Eu-LnPO
4The contrast of core-shell structured fluorescence particulate X-ray diffractogram.
A is Y among the figure
2O
3: the diffraction peak that Eu produced, B is LnPO
4The diffraction peak that is produced.
Under Fig. 3 ultraviolet excitation, the photoluminescence photo of fluorescent grain.Among the figure from left to right each sample be respectively: pure Y
2O
3: Eu, Y
2O
3: Eu-LnPO
4Core-shell particle ((Y from left to right
2O
3: Eu): LnPO
4Mol ratio be respectively 1: 0.4,1: 0.8,1: 1,1: 2.), pure LnPO
4
Under Fig. 4 ultraviolet excitation, Y
2O
3: Eu-LnPO
4Core-shell structured fluorescence particulate laser co-focusing figure.
Embodiment
Embodiment 1
(Y
2O
3: Eu): LnPO
4Mol ratio be the preparation of 1: 1 core-shell structured fluorescence granular material
● with 0.25molLa
2O
3, 0.30molTb (NO
3)
36H
2O, 0.15molCe (NO
3)
36H
2O is dissolved in the rare nitric acid of 0.01M, is mixed with rare-earth ion solution.
● respectively get from the rare-earth ion solution that the above-mentioned the first step is prepared in right amount, be mixed with mixed rare earth ionic solution 30mL, the mixed rare earth ionic solution middle-weight rare earths ionic total amount that is made into is 2.5mmol, wherein La
3+, Ce
3+, Tb
3+Amount of substance be respectively 1.425mmol, 0.725mmol, 0.35mmol.And with salt acid for adjusting pH value to 3.0～4.0, the pH value is measured by accurate pH test paper.
● take by weighing the 2.5mmol tripoly phosphate sodium STPP, it is dissolved in the 20mL water, successively the pH value of solution value is adjusted to about 3.0, be mixed with sodium tripolyphosphate solution with 6M and 1M hydrochloric acid.The pH value is measured by accurate pH test paper.
● continue to stir with magnetic stirring apparatus, stirring velocity is 200 rev/mins, and above-mentioned second mixed rare earth ionic solution that goes on foot is dropwise added in the tripolyphosphate sodium water solution in above-mentioned the 3rd step, and rate of addition is 1 droplet/second, obtains clear and transparent mixed solution.In dripping the process of rare-earth ion solution, be the hydrochloric acid soln pH value of regulator solution at any time of 0.1M with concentration, it is remained on about 3.0.The pH value is measured by accurate pH test paper.
● take by weighing the Y that size is 4～8 μ m
2O
3: Eu inner core particles material 2.5mmol, insert it in mixing solutions in above-mentioned the 4th step.
● keep stirring with magnetic stirring apparatus, stirring velocity is 200 rev/mins, and the above-mentioned the 5th mixing solutions that goes on foot was placed 90 ℃～98 ℃ following sustained reactions 3～5 hours.
● reaction is cooled to room temperature with system after finishing, and leaves standstill about 10min, filtering with microporous membrane with 0.22 μ m goes out precipitation, gained precipitate with deionized water washing 4～5 times places 30 ℃ of vacuum drying oven dried overnight more than 12 hours the gained precipitation, makes the core-shell structured fluorescence material granule.
● (SIRION, FEI is Holland) to the Y as kernel with scanning electron microscope
2O
3: Eu particle and Y
2O
3: Eu-LnPO
4The core-shell structured fluorescence particle has carried out morphology analysis (seeing accompanying drawing 1), the result show form nucleocapsid structure after, particle surface is no longer smooth, and particle size obviously increases, the size of core-shell particle is about 8-14 μ m.With X-ray diffractometer (RigakuD/max-rA Japan) has analyzed particulate phase composite before and after the formation nucleocapsid structure, and (seeing accompanying drawing 2) result show, form nucleocapsid structure after, the Y of internal layer
2O
3: Eu is wrapped up substantially fully, and its corresponding diffraction peak intensity descends greatly.Meanwhile, new peak occurred in the X-ray diffractogram of core-shell particle, their position is just in time corresponding to the LnPO of shell
4With the laser co-focusing instrument (LSM 510 META, Carl Zeiss Germany) observes the core-shell structured fluorescence particle, (seeing accompanying drawing 4) found that the part that glows and the part of green light overlap on the same position fully, this explanation has formed Y really
2O
3: Eu-LnPO
4Nucleocapsid structure.
Embodiment 2-4
(Y
2O
3: Eu): LnPO
4Mol ratio 1: 0.4,1: 0.8,1: 1,1: 2 core-shell structured fluorescence granular material preparation was with reference to the preparation method of embodiment 1, that different is (Y
2O
3: Eu): LnPO
4Mol ratio be 1: 0.4,1: 0.8,1: 2, the size of the core-shell structured fluorescence granular material of acquisition was 6～16 μ m.
(254nm) excites Y with UV-light
2O
3: Eu-LnPO
4Core-shell structured fluorescence particle (seeing accompanying drawing 3), among the figure from left to right each sample be respectively: pure Y
2O
3: Eu, Y
2O
3: Eu-LnPO
4Core-shell particle ((Y from left to right
2O
3: Eu): LnPO
4Mol ratio be respectively 1: 0.8,1: 1,1: 21: 0.4), pure LnPO
4Discovery is along with (Y
2O
3: Eu): LnPO
4The reducing of mol ratio numerical value, core-shell structured fluorescence particulate emission light medium green colour content increases gradually, red composition reduces gradually, can reach the adjustable purpose of core-shell structured fluorescence particle light-emitting by the ratio of regulating stratum nucleare, shell.
Claims (5)
1, a kind of luminous adjustable core-shell structured fluorescence granular material is characterized in that stratum nucleare and shell are independently luminescent material, and inner nuclear material is the Y that glows
2O
3: Eu micron particle, sheating material are the LnPO of green light
4Fluorescent material, LnPO
4=LaPO
4: Ce, Tb; Described kernel size is 4～8 μ m, and the size of core-shell particle is 6～16 μ m; Described inner nuclear material Y
2O
3: the mol ratio of Eu is: 95: 5～91: 9; La in the described sheating material: Ce: the mol ratio of Tb material is: 0.60: 0.27: 0.13～0.55: 0.30: 0.15; Described (Y
2O
3: Eu): LnPO
4Mol ratio be: 1: 0.4～1: 2.
2, the preparation method of fluorescence granular material according to claim 1 is characterized in that La: Ce: the mol ratio of Tb material is 0.57: 0.29: 0.14.
3, the preparation method of fluorescence granular material according to claim 1 is characterized in that inner nuclear material Y
2O
3: Eu and sheating material LnPO
4Mol ratio be 1: 1.
4, the preparation method of fluorescence granular material according to claim 1 is characterized in that inner nuclear material Y
2O
3: the Eu mol ratio is 93: 7.
5, the Y of the described nucleocapsid structure of claim 1
2O
3: Eu-LnPO
4The preparation method of fluorescence granular material is characterized in that the mixed rare earth ionic solution of preparation sheating material is dropwise added in the tripolyphosphate sodium water solution, adds the Y as kernel again
2O
3: the Eu micron particle, under the certain reaction condition, tripoly phosphate sodium STPP progressively after the hydrolysis formed phosphate anion combine with rare earth ion in the solution, with Y
2O
3: the Eu micron particle is that core growth forms LnPO
4Shell; Through cooling, filtration, washing, collect the fluorescence granular material that obtains nucleocapsid structure after the vacuum-drying; Comprise the steps:
Preparation rare-earth ion solution: respectively with 0.04～0.30mol La
2O
3, 0.08～0.60mol Tb (NO
3)
36H
2O, 0.08～0.60mol Ce (NO
3)
36H
2O is dissolved in the rare nitric acid of 1L0.01M, is mixed with volumetric molar concentration to be: the rare-earth ion solution of 0.08～0.60M;
Preparation mixed rare earth ionic solution: from the rare-earth ion solution that the above-mentioned the first step is prepared, by La: Ce: the mol ratio of Tb material was mixed with mixed rare earth ionic solution in 0.60: 0.27: 0.13～0.55: 0.30: 0.15, with the salt acid for adjusting pH value is 2.5～3.5, the pH value is measured by accurate pH test paper, obtains mixed rare earth ionic solution;
The preparation sodium tripolyphosphate solution: take by weighing tripoly phosphate sodium STPP, it is soluble in water, successively the pH value of solution is adjusted to 2.5～3.5 with 6M and 1M hydrochloric acid, be mixed with the sodium tripolyphosphate solution that volumetric molar concentration is 0.04～0.06M;
Mixed rare earth ionic solution with above-mentioned second step, continuing under the condition of stirring, by mixed rare earth ionic solution and sodium tripolyphosphate solution mol ratio be: dropwise added in 1: 1～1: 1.4 in the tripolyphosphate sodium water solution in above-mentioned the 3rd step, rate of addition is 1 droplet/second, stir, obtain preparing the mixing solutions of sheating material;
Take by weighing the Y that size is 4～8 μ m
2O
3: the Eu micron particle, press inner nuclear material Y
2O
3: Eu and sheating material LnPO
4Mol ratio be to carry out weighing in 1: 0.4～1: 2, insert in the mixing solutions of above-mentioned the 4th step preparation sheating material, when keeping stirring, placed 90 ℃～98 ℃ following sustained reactions 3～5 hours;
After reaction finishes, system is cooled to room temperature, goes out precipitation with the filtering with microporous membrane of 0.22 μ m, the gained precipitate with deionized water repeatedly thoroughly after the washing, placed 30 ℃ of vacuum drying ovens dryings 12～24 hours, obtained Y
2O
3: Eu-LnPO
4Nuclear-shell fluorescence granular material.
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