CN106947484B - A kind of rear-earth-doped NaYF of dendroid4The preparation method and purposes of up-conversion - Google Patents
A kind of rear-earth-doped NaYF of dendroid4The preparation method and purposes of up-conversion Download PDFInfo
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- CN106947484B CN106947484B CN201710241220.7A CN201710241220A CN106947484B CN 106947484 B CN106947484 B CN 106947484B CN 201710241220 A CN201710241220 A CN 201710241220A CN 106947484 B CN106947484 B CN 106947484B
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 129
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 42
- 241000555268 Dendroides Species 0.000 claims abstract description 36
- -1 rare earth ion Chemical class 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010345 tape casting Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 63
- 239000000243 solution Substances 0.000 claims description 37
- 239000007864 aqueous solution Substances 0.000 claims description 32
- 235000019441 ethanol Nutrition 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 20
- 150000001225 Ytterbium Chemical class 0.000 claims description 18
- 150000003746 yttrium Chemical class 0.000 claims description 18
- 150000000917 Erbium Chemical class 0.000 claims description 11
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 11
- 150000002910 rare earth metals Chemical class 0.000 claims description 11
- 239000001509 sodium citrate Substances 0.000 claims description 11
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 11
- 229940038773 trisodium citrate Drugs 0.000 claims description 10
- 239000003945 anionic surfactant Substances 0.000 claims description 9
- 239000003093 cationic surfactant Substances 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 8
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical class [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims description 7
- 150000000922 Holmium Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 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 3
- 239000012467 final product Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical group CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical compound CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 claims description 2
- 229960004830 cetylpyridinium Drugs 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical group [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 2
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical group Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- WDVGLADRSBQDDY-UHFFFAOYSA-N holmium(3+);trinitrate Chemical compound [Ho+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WDVGLADRSBQDDY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- LLZBVBSJCNUKLL-UHFFFAOYSA-N thulium(3+);trinitrate Chemical compound [Tm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LLZBVBSJCNUKLL-UHFFFAOYSA-N 0.000 claims description 2
- ILOTUXNTERMOJL-UHFFFAOYSA-K thulium(iii) chloride Chemical group Cl[Tm](Cl)Cl ILOTUXNTERMOJL-UHFFFAOYSA-K 0.000 claims description 2
- PYOOBRULIYNHJR-UHFFFAOYSA-K trichloroholmium Chemical group Cl[Ho](Cl)Cl PYOOBRULIYNHJR-UHFFFAOYSA-K 0.000 claims description 2
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 2
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical group [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 32
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000004020 luminiscence type Methods 0.000 abstract description 4
- 239000010409 thin film Substances 0.000 abstract description 4
- 229920006280 packaging film Polymers 0.000 abstract description 2
- 239000012785 packaging film Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 150000001450 anions Chemical class 0.000 abstract 1
- 150000001768 cations Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 33
- 239000000047 product Substances 0.000 description 30
- 239000000725 suspension Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 17
- 239000013078 crystal Substances 0.000 description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 230000005284 excitation Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 239000002096 quantum dot Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000012190 activator Substances 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920001109 fluorescent polymer Polymers 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
- C09K11/7773—Halogenides with alkali or alkaline earth metal
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a kind of rear-earth-doped NaYF of dendroid4Up-conversion and its preparation method and application.It adjusts the hydro-thermal method under being situated between jointly by anion/cation surfactant, synthesizes high-crystallinity, pure hexagonal phase, and good water solubility, the rare earth ion doped NaYF of the high dendroid of fluorescence intensity4Up-conversion.By the NaYF of synthesis4Up-conversion its as functional stuffing, rare earth ion doped NaYF is prepared by the tape casting4Up-conversion/PVA laminated film, can make PVA film have up-conversion luminescence performance in the case where not influencing thin-film transparent, can be used as anti-counterfeit packaging film use.
Description
Technical field
The invention discloses a kind of preparation methods of up-conversion, and in particular to a kind of rear-earth-doped NaYF of dendroid4
The preparation method and purposes of up-conversion；Belong to nanocomposite technical field.
Background technique
The continuous development of market economy, Commodity Competition is fiercer, the normal economy of fake and inferior commodities very disruptive
Order, package anti-counterfeiting technology alternate rapid as the important means technology of commodity counterfeit prevention.Anti-counterfeiting technology common at present has: printing
Technique is anti-fake, code anti-fake, optical anti-counterfeiting, structural anti false and atomic nucleus double card anti-counterfeiting technology etc..Fluorescence falsification preventing is materials chemistry
The important branch of anti-counterfeiting technology, main Application in Anti-counterfeiting form have anti-forgery ink, anti-counterfeit paint, false-proof film, anti-counterfeiting paper, anti-fake
Fiber etc. is several.Common fluorescence falsification preventing material has organic fluorescent dye, quantum dot, rare earth compounding and rear-earth-doped go up to turn
Change fluorescent material etc..Organic fluorescent dye, quantum dot and rare earth compounding belong to down-conversion luminescent material, higher poison
Property, transreplication and wider fluorescence emission peak limit the application in fluorescence falsification preventing.Rear-earth-doped up-conversion luminescent material
The higher shortwave radiation of energy can be issued, is anti-stoke luminescent material, compares under the lower long-wave radiation excitation of energy
In other fluorescent materials, rare earth up-conversion has special, efficient luminescent properties, it is difficult to replicate, detection is simple, fast light drift
White, toxicity is low, and stability is high and is widely used.Rear-earth-doped up-conversion luminescent material is usually by activator, sensitizer and base
Three parts of matter form.Rare earth fluoride especially NaYF4, due to its own lower phonon energy, can be effectively reduced
The radiationless relaxation rate of transition material, it is considered to be one of optimum substrate material.
Currently, NaYF4Up-conversion luminescence nano particle is concentrated mainly on for fluorescence falsification preventing and prepares fluorescent ink.Middle promulgated by the State Council
Bright patent CN201610308927.0 discloses silk-screen printing rare earth up-conversion luminescence ink and preparation method thereof and anti-fake answers
With being applied using rare earth up-conversion luminescent material as anti-forgery ink.It is this to be based on rear-earth-doped NaYF4Up-conversion
Fluorescent ink is used for fluorescence falsification preventing, and a most significant problem is, rear-earth-doped NaYF4Up-conversion fluorescent ink it is steady
It is qualitative, i.e., due to rear-earth-doped NaYF4Up-conversion itself is water-fast, oil resistivity is bad, and anti-fake mark is caused to be easily lost, from
And influence its anti-counterfeiting performance.Fluorescent material is embedded into polymeric film substrates prepare fluorescent polymer film be solve it is above-mentioned
The effective ways of problem.Also, film is widely used in packaging, prepares fluorescent material THIN COMPOSITE using rare earth up-conversion
Film has good application prospect in package anti-counterfeiting field.Inorganic upconverting fluorescent material is dispersed in main film body matrix
In, because of the few transparency for not influencing film of fluorescent material dosage, only under the excitation of specific infrared light (wavelength 980nm)
Fluorescence, good concealment can be shown, hardly possible copies the purpose, it can be achieved that anti-fake.Chinese invention patent CN201410720118.9 is announced
A kind of preparation method of electrostatic spinning fluorescence PVA nano fibrous membrane, it was also proposed that it is used as fluorescence falsification preventing film, but its
The process for preparing fluorescent nano material is complicated, and needs to carry out modified be just able to achieve in surface and be blended with PVA.It is warmed compared to height
Decomposition method, hydro-thermal method prepare NaYF4Up-conversion has the product good water solubility that synthesis condition is mild, synthesizes, and yield phase
To it is higher the advantages that.NaYF is synthesized in hydro-thermal method4In up-conversion, differential responses condition has very big shadow to the pattern of product
It rings.And prepare in organic-inorganic materials, the microstructure of inorganic nano material is also to influence itself and polymeric matrix
The key factor of material compatibility.Dendritic structure makes it be easy to be blended to be formed with basis material because of its special geometry
Multifunctional composite.Hydro-thermal method under Tsinghua University professor Li Yadong is situated between by cetyl trimethylammonium bromide tune synthesizes
Dendroid NaYF with α (cube) phase4: Er3+/Yb3+Material, and it is applied to polystyrene fluorescence composite material
Preparation (Inorg.Chem.2007,46,6050-6055).Compared to the NaYF of α (cube) phase4Up-conversion, β (six
Side) phase NaYF4Up-conversion has better up-conversion luminescence performance.Therefore, suitable hydro-thermal method technology path is explored
Synthesis has β (six sides) phase dendroid NaYF4Up-conversion, for developing NaYF4Up-conversion/polymer composite
Material, the preparation process for simplifying the prior art are of great significance.
Summary of the invention
For being difficult to obtain β (six sides) phase dendroid NaYF in the prior art by hydro-thermal method4Up-conversion lacks
It falls into, it is high it is an object of the invention to be to provide a kind of good water solubility, fluorescence intensity, have β (six sides) phase dendroid dilute
Native ion doping NaYF4The preparation method of up-conversion.
Another object of the present invention is to be to provide a kind of rare earth ion doped NaYF of high quality dendroid4On
Application of the transition material in preparation fluorescent composite thin film.The rare earth ion doped NaYF of dendroid4Up-conversion has good
Fluorescence property, be easy to be blended with polymeric substrate dendroid micro-structure, good water solubility the advantages that, the fluorescence falsification preventing of preparation is thin
There is film security feature easily to detect, and hardly possible is imitated, and performance is stablized, and have good application prospect in package anti-counterfeiting field.
In order to achieve the above technical purposes, the present invention provides one kind to have β (six sides) phase dendroid rear-earth-doped
NaYF4The preparation method of up-conversion, this method be in rare earth salt aqueous solution, be added anionic surfactant solution,
Cationic surfactant solution and NaF aqueous solution are transferred in water heating kettle after mixing evenly, regulation system pH value to 1~2,
Hydro-thermal reaction is carried out at a temperature of 180 DEG C~240 DEG C to get the rear-earth-doped NaYF of hexagonal phase dendroid4Up-conversion.
The rear-earth-doped NaYF of dendroid is prepared in hydro-thermal method in technical solution of the present invention4During up-conversion, close
Key is for anionic surfactant and cationic surfactant to be applied in combination, and on the one hand can promote NaYF4By metastable state
The opposite thermostabilization state in four directions hexagonal phase transformation, prepare pure hexagonal phase state up-conversion；On the other hand the two is utilized
It acts synergistically, the end branching in induced material growth course, and then grow dendroid micro-structure.Anionic surfactant
Chelate is formed by coordination with rare earth ion, it is in hydrothermal reaction process that the nucleation stage of crystal and crystal is raw
Long stage separation, to obtain highly crystalline product.Coordination ion is adsorbed on plane of crystal, and crystal is made to be evenly dispersed in reactant
In system, the surface free energy of reaction system is improved, promotes transformation of the crystal from cubic phase to hexagonal phase state.Cationic surface is living
Property agent, plays competitive coordination in system, can weaken that single complexant may cause by excessive concentration to crystal from
The inhibiting effect of cubic opposite hexagonal phase transformation, while can be improved the surface free energy in system, reduce the energy of crystal transition
Barrier is measured, compared with synthesizing pure hexagonal phase crystal under mild reaction conditions.Furthermore cationic surfactant shape in the reaction system
At micella, by inhibiting anionic surfactant to be adsorbed on the anisotropic growth trend that particular crystal plane is formed, to crystal
Prolong single direction growth and generate constraint, and the branching of induced crystal end, and then grows dendritic structure.
Preferred scheme, the anionic surfactant solution are trisodium citrate aqueous solution.
Preferred scheme, the cationic surfactant solution are halogenated phosphates ethanol solution.
Preferred scheme, the molar ratio of trisodium citrate and rare-earth salts is 0.5~1.5 in the citric acid three sodium solution:
1。
Preferred scheme, molar ratio of the halogenated phosphates Chlorine in Solution for cetyl pyridinium and rare-earth salts
For 0.4~1.0:1.
Preferred scheme, the molar ratio of NaF and rare-earth salts is 12~18:1 in the NaF aqueous solution.
More preferably scheme, the concentration of the anionic surfactant are 0.07~0.20molL-1。
More preferably scheme, the cationic surfactant solution concentration are 0.02~0.05molL-1。
More preferably scheme, the solubility of NaF aqueous solution are 1~1.5molL-1。
More preferably scheme, the volume ratio of water and ethyl alcohol is 2~4:2 in system.
Preferred scheme includes yttrium salt, ytterbium salt, M1 salt and M2 salt in the rare-earth salt solution；Yttrium salt, ytterbium salt, M1 salt and
The molar ratio of M2 salt is (90-x-y): 10:x:y, 0≤x, y < 3,2≤x+y < 5；
M1 salt and M2 salt are independently selected from erbium salt, thulium salt or holmium salt.
Technical solution of the present invention is adjustable to obtain having difference by changing the proportionate relationship between various rare-earth salts
The up-conversion of up-conversion fluorescence color.It is adjustable to be had by adjusting doping of the up-conversion in PVA
The fluorescence membrane of different fluorescence intensities, and then a variety of PVA anti-counterfeit packaging films with different fluorescent characteristics can be obtained.
More preferably scheme, the ytterbium salt are ytterbium chloride and/or ytterbium nitrate.
More preferably scheme, the yttrium salt are yttrium chloride and/or yttrium nitrate.
More preferably scheme, the erbium salt are erbium chloride and/or erbium nitrate.
More preferably scheme, the thulium salt are thulium chloride and/or thulium nitrate.
More preferably scheme, the holmium salt are holmium chloride and/or holmium nitrate.
Preferred scheme, time of the hydro-thermal reaction is 8~for 24 hours.
Preferred scheme, rare-earth salt solution are rare earth salt aqueous solution.
Preferred scheme, system pH are adjusted using concentrated nitric acid.By the way that pH value of reaction system is adjusted to 1~2 available branch
Shape micro-structure product, pH value, which is greater than 2 but forms draw ratio small column and the spherical product mixed, pH value when being acid, to be increased to
It will appear by-product when alkaline and be unfavorable for reaction progress.
The rear-earth-doped NaYF of dendroid of technical solution of the present invention preparation4Up-conversion microscopic appearance is dendroid,
Crystal phase is pure hexagonal phase, and crystallinity is high, good water solubility.
The present invention also provides a kind of rear-earth-doped NaYF of dendroid4The application of up-conversion, the application are by branch
The rear-earth-doped NaYF of shape4Up-conversion is as fluorescent functional applying filler in preparation fluorescent composite thin film.
Preferred scheme, the rear-earth-doped NaYF of dendroid4Up-conversion is blended with PVA, and dissolution is prepared by the tape casting
Fluorescence PVA film.
More preferably scheme, by the rare earth ion doped NaYF of dendroid4Up-conversion and PVA in mass ratio (0.1~
4): 100 mixed dissolutions, cooling, tape casting to get.
More preferably scheme, tape casting gained laminated film is with a thickness of 0.06mm~0.2mm.
Compared with the prior art, technical solution of the present invention bring the utility model has the advantages that
1, technical solution of the present invention is situated between by using Yin/Yang double ion surfactant tune, and obtain has six sides for the first time
The rear-earth-doped NaYF of the dendroid of phase4Up-conversion.Up-conversion with pure hexagonal phase is than cubic phase or four or six sides
The up-conversion mutually mixed has higher fluorescence intensity.
2, technical solution of the present invention passes through the hydro-thermal method one-step synthesis rear-earth-doped NaYF of dendroid4Up-conversion,
Synthesis step is simple, and mild condition is conducive to industrialized production.
3, the up-conversion of the dendroid hexagonal phase of technical solution of the present invention preparation has dendritic structure, and water
Dissolubility is good, and fluorescence intensity is high, and the preparation of PVA film is used for as fluorescence identifying functional stuffing, is shown following excellent
Performance: its be uniformly dispersed in water-solubility PVA film substrate (and existing rare earth from doping NaYF4Up-conversion needs pair
Its surface modification is realized using the particular geometry of its modification and is efficiently blended), do not influence thin-film transparent, anti-fake concealment
It is good, it is not easy to be imitated；The pure hexagonal phase state NaYF of high-crystallinity4Up-conversion, fluorescence intensity is high, and anti-counterfeiting characteristic is easy to identify；Tree
Dendritic micro-structure is tightly combined with substrate, and performance is stablized, and anti-counterfeiting characteristic is not easy to lose；With rare earth ion doped NaYF4As glimmering
Luminescent material, compared to fluorescent materials such as rare earth compounding, quantum dot, organic dyestuff, its optical property is more stable, floats more resistant to light
It is white, thus be more suitable for as anti-counterfeit package application.
Detailed description of the invention
[Fig. 1] is the rear-earth-doped NaYF of dendroid prepared by embodiment 14The XRD test result of up-conversion；
[Fig. 2] is the rear-earth-doped NaYF of dendroid prepared by embodiment 14Up-conversion is under 980nm laser excitation
Fluorescence spectra；
[Fig. 3] is the rear-earth-doped NaYF of dendroid prepared by embodiment 14Microscopic appearance under up-conversion SEM characterization
Figure；
[Fig. 4] is the rear-earth-doped NaYF of dendroid prepared by embodiment 14Microscopic appearance under up-conversion TEM characterization
And electron diffraction diagram；
[Fig. 5] is the up-conversion/PVA laminated film for preparing of embodiment 1 under natural lighting and 980nm laser irradiation
Under digital photograph；
[Fig. 6] is rear-earth-doped NaYF prepared by comparative example 64Microscopic appearance figure under up-conversion SEM characterization；
[Fig. 7] is rear-earth-doped NaYF prepared by fullsized embodiment 74Microscopic appearance figure under up-conversion SEM characterization.
Specific embodiment
Further detailed description is done to the present invention below with reference to embodiment, embodiments of the present invention are not limited thereto.
Embodiment 1
(1) in 100mL round-bottomed flask, 0.1 molL of 10mL the preparation of dendroid up-conversion: is added-1Rare earth
Saline solution (wherein yttrium salt: ytterbium salt: the molar ratio of erbium salt is 0.88:0.10:0.02), 7.5mL 0.1molL-1Citric acid
Three sodium water solutions and 20mL 0.025molL-1Halogenated phosphates ethanol solution, stirs 30min at room temperature, obtains
Milky suspension.Then, 12mL 1.0molL is added dropwise into the milky suspension-1NaF aqueous solution, is stirred at room temperature
Mix 1h.Resulting suspension is transferred in 100mL hydrothermal reaction kettle, and 1~1.5mL concentrated nitric acid regulation system pH=is added
1.5, reaction 12h is stood in 180 DEG C of baking oven.After completion of the reaction, reaction system cooled to room temperature, centrifuge separation
(12000 rpm, 10min) and with ethanol washing (three times), product obtains rear-earth-doped NaYF in 60 DEG C of vacuum drying 6h4On
Transition material.The XRD spectrum of products therefrom is as shown in Figure 1, all diffraction maximum positions and relative intensity and hexagonal phase NaYF4Matching
Well, without other phase miscellaneous peaks, and peak shape is sharp, illustrates that the product is highly crystalline pure hexagonal phase NaYF4Material；Products therefrom exists
Fluorescence spectra under 980nm laser excitation is as shown in Fig. 2, the wavelength energy and Er of four emission peak positions in spectrogram3+
's2H9/2-4I15/2,2H11/2-4I15/2, 4S3/2-4I15/2With4F9/2-4I15/2Energy level transition energy it is corresponding, illustrate product
Fluorescence is apparently higher than purple light with red light wavelength model by activator Er emission of ions, positioned at the emission peak intensity of green wavelength
The emission peak enclosed, therefore strong green emitting is presented in the aqueous solution of product under 980nm exciting light；The scanning electricity of products therefrom
Mirror figure shows skeleton pattern as shown in figure 3, product can be observed in figure, and pattern has Multivariate characteristics, including
Simple three arm, the patterns such as four arms, while further including other more complicated multi-arm dendroid patterns.Typical multi-arm branch
The TEM picture of shape pattern as shown in figure 4, and the diffraction pattern of crystal typical dot chart is presented, show that the dendroid of synthesis is dilute
Soil doping NaYF4Up-conversion is high-crystallinity monocrystal material.
(2) in the round-bottomed flask of 250mL, 90 mL deionized waters up-conversion/PVA laminated film preparation: are added
With dendroid up-conversion obtained in 0.2g above-mentioned steps, after ultrasonic 20min, 10g PVA is added, is slowly stirred, to PVA
It after complete swelling, is warming up to 90 DEG C and accelerates mixing speed, continue to stir 2.5h, generate laminated film stoste, after standing cooling
Film stoste is cast again uniformly on mold, is dried in vacuo 12h at 40 DEG C to obtain the final product.Laminated film swashs in natural light and 980nm
Digital photograph under two kinds of light environments of light is as shown in Figure 5, it is seen that the laminated film is transparent under natural lighting, swashs in 980nm
Capable of emitting strong green fluorescence under light excitation.
Embodiment 2
The preparation of dendroid up-conversion: in 100mL round-bottomed flask, 10mL 0.1molL is added-1Rare earth salt water
Solution (wherein yttrium salt: ytterbium salt: the molar ratio of thulium salt is 0.88:0.10:0.02), 0.12 molL of 7.5mL-1Trisodium citrate
Aqueous solution and 20mL 0.03molL-1Halogenated phosphates ethanol solution, stirs 30min at room temperature, obtains milky
Suspension.Then, 12mL 1.2molL is added dropwise into the milky suspension-1The aqueous solution of NaF, is stirred at room temperature
1h.Resulting suspension is transferred in 100mL hydrothermal reaction kettle, and 1~1.5mL concentrated nitric acid regulation system pH=is added
1.5, reaction 12h is stood in 180 DEG C of baking oven.After completion of the reaction, reaction system cooled to room temperature, centrifuge separation
(12000rpm, 10min) and with ethanol washing (three times), it is rear-earth-doped that product in 60 DEG C of vacuum drying 6h obtains dendroid
NaYF4Up-conversion.
The preparation of up-conversion/PVA laminated film: in the round-bottomed flask of 250mL, be added 90mL deionized water and
Dendroid up-conversion obtained in 0.2g above-mentioned steps after ultrasonic 20min, is added 10 g PVA, is slowly stirred, to PVA
It after complete swelling, is warming up to 90 DEG C and accelerates mixing speed, continue to stir 2.5h, generate laminated film stoste, after standing cooling
Film stoste is cast again uniformly on mold, is dried in vacuo 12h at 40 DEG C to obtain the final product.Gained up-conversion and upper conversion material
Material/PVA laminated film is blue under 980nm exciting light to shine.
Embodiment 3
Other conditions are same as Example 1, and the molar ratio of rare earth salt aqueous solution is adjusted to yttrium salt by difference: ytterbium salt:
The molar ratio of holmium salt is that 0.88:0.10:0.02, gained up-conversion and up-conversion/PVA laminated film swash in 980nm
Shining lower is in green emitting.
Embodiment 4
Other conditions are same as Example 1, and the molar ratio of rare earth salt aqueous solution is adjusted to yttrium salt by difference: ytterbium salt:
Thulium salt: the molar ratio of erbium salt is 0.86:0.10:0.02:0.02, gained up-conversion and up-conversion/PVA laminated film
It shines under 980nm exciting light in yellow green.
Embodiment 5
Other conditions are same as Example 1, and the molar ratio of rare earth salt aqueous solution is adjusted to yttrium salt by difference: ytterbium salt:
The molar ratio of thulium salt is that 0.65:0.30:0.5, gained up-conversion and up-conversion/PVA laminated film are excited in 980nm
It takes on a red color under light luminous.
Embodiment 6
Other conditions are same as Example 1, and difference is during the preparation of up-conversion/PVA laminated film
0.1g dendroid up-conversion is added, the THIN COMPOSITE under 980nm laser excitation with relatively weak green emitting can be obtained
Film.
Embodiment 7
Other conditions are same as Example 2, and difference is during the preparation of up-conversion/PVA laminated film
0.4g dendroid up-conversion is added, the laminated film under 980nm laser excitation with stronger blue-light-emitting can be obtained.
Comparative example 1
The preparation of up-conversion: in 100mL round-bottomed flask, 10mL 0.1molL is added-1Rare earth salt aqueous solution (its
Middle yttrium salt: ytterbium salt: the molar ratio of erbium salt is 0.88:0.10:0.02), 7.5mL 0.1molL-1The aqueous solution of trisodium citrate
And 20mL ethyl alcohol, 30min is stirred at room temperature, obtains milky suspension.Then, it is added dropwise into the milky suspension
12mL 1mol·L-1The aqueous solution of NaF, stirs 1h at room temperature.Resulting suspension is transferred in 100mL hydrothermal reaction kettle,
And 1~1.5mL concentrated nitric acid regulation system pH=1.5 is added, reaction 12h is stood in 180 DEG C of baking oven.After completion of the reaction, instead
Answer system cooled to room temperature, be centrifugated (12000rpm, 10min) and use ethanol washing (three times), product in 60 DEG C very
The dry 6h of sky obtains white powder, and products therefrom is four hexagonal phase hybrid materials.
Comparative example 2
The preparation of up-conversion: in 100mL round-bottomed flask, 10mL 0.1molL is added-1Rare earth salt aqueous solution (its
Middle yttrium salt: ytterbium salt: the molar ratio of erbium salt is 0.88:0.10:0.02), 7.5mL water and 20mL 0.025molL-1Chloro ten
Six alkyl pyridine ethanol solutions, stir 30min at room temperature, obtain milky suspension.Then, into the milky suspension by
It is added dropwise to 12mL 1molL-1The aqueous solution of NaF, stirs 1h at room temperature.Resulting suspension is transferred to 100mL hydro-thermal reaction
In kettle, and 1~1.5mL concentrated nitric acid regulation system pH=1.5 is added, reaction 12h is stood in 180 DEG C of baking oven.End of reaction
Afterwards, reaction system cooled to room temperature, is centrifugated (12000rpm, 10min) and with ethanol washing (three times), and product is in 60
DEG C vacuum drying 6h obtains white powder, and products therefrom is four hexagonal phase hybrid materials.
Comparative example 3
The preparation of up-conversion: in 100mL round-bottomed flask, 10mL 0.1molL is added-1Rare earth salt aqueous solution (its
Middle yttrium salt: ytterbium salt: the molar ratio of erbium salt is 0.88:0.10:0.02), 7.5mL 0.1molL-1The aqueous solution of trisodium citrate
And 20mL 0.025molL-1Halogenated phosphates ethanol solution, stirs 30min at room temperature, and it is suspended to obtain milky
Liquid.Then, 8mL 1molL is added dropwise into the milky suspension-1The aqueous solution of NaF, stirs 1h at room temperature.By gained
Suspension be transferred in 100mL hydrothermal reaction kettle, and be added 1~1.5mL concentrated nitric acid regulation system pH=1.5, in baking oven
Reaction 12h is stood at 180 DEG C.After completion of the reaction, reaction system cooled to room temperature, centrifuge separation (12000rpm,
10min) and with ethanol washing (three times), product obtains white powder, products therefrom NaYF in 60 DEG C of vacuum drying 6h4With
NaYF3Mixture.
Comparative example 4
The preparation of up-conversion: in 100mL round-bottomed flask, 10mL 0.1molL is sequentially added-1Rare-earth salts is water-soluble
Liquid (wherein yttrium salt: ytterbium salt: the molar ratio of erbium salt is 0.88:0.10:0.02), 7.5mL 0.1molL-1The water of trisodium citrate
Solution and 20mL 0.025molL-1Halogenated phosphates ethanol solution, stirs 30min at room temperature, obtains milky
Suspension.Then, 12mL 1molL is added dropwise into the milky suspension-1The aqueous solution of NaF, stirs 1h at room temperature.
Resulting suspension is transferred in 100mL hydrothermal reaction kettle, and 1~1.5mL concentrated nitric acid regulation system pH=1.5 is added, in
Reaction 12h is stood in 150 DEG C of baking oven.After completion of the reaction, reaction system cooled to room temperature, centrifuge separation
(12000rpm, 10min) and with ethanol washing (three times), product obtains white powder, products therefrom in 60 DEG C of vacuum drying 6h
The material mixed for four hexagonal phases.
Comparative example 5
The preparation of up-conversion: in 100mL round-bottomed flask, 10mL 0.1molL is sequentially added-1Rare-earth salts is water-soluble
Liquid (wherein yttrium salt: ytterbium salt: the molar ratio of erbium salt is 0.88:0.10:0.02), 7.5mL 0.1molL-1The water of trisodium citrate
Solution and 20mL 0.025molL-1Halogenated phosphates ethanol solution, stirs 30min at room temperature, obtains milky
Suspension.Then, 12mL 1molL is added dropwise into the milky suspension-1The aqueous solution of NaF, stirs 1h at room temperature.
Resulting suspension is transferred in 100mL hydrothermal reaction kettle, and 1~1.5mL concentrated nitric acid regulation system pH=1.5 is added, in
Reaction 5h is stood in 180 DEG C of baking oven.After completion of the reaction, reaction system cooled to room temperature, centrifuge separation (12000rpm,
10min) and with ethanol washing (three times), product obtains white powder in 60 DEG C of vacuum drying 6h, and products therefrom is four hexagonal phases
The material mixed.
Comparative example 6
The preparation of up-conversion: in 100mL round-bottomed flask, 10mL 0.1molL is sequentially added-1Rare-earth salts is water-soluble
Liquid (wherein yttrium salt: ytterbium salt: the molar ratio of erbium salt is 0.88:0.10:0.02), 7.5mL 0.1molL-1The water of trisodium citrate
Solution and 20mL 0.025molL-1Halogenated phosphates ethanol solution, stirs 30min at room temperature, obtains milky
Suspension.Then, 12mL 1molL is added dropwise into the milky suspension-1The aqueous solution of NaF, stirs 1h at room temperature.
Resulting suspension is transferred in 100mL hydrothermal reaction kettle, 0.5~1mL concentrated nitric acid regulation system pH=3 is added, in 180 DEG C
Baking oven in stand reaction 12h.After completion of the reaction, reaction system cooled to room temperature, centrifuge separation (12000rpm,
10min) and with ethanol washing (three times), product obtains white powder, the scanning electron microscope of products therefrom in 60 DEG C of vacuum drying 6h
Figure is as shown in fig. 6, the product obtained when pH value of reaction system is 3 is the small column of draw ratio and some spheroidal materials.
Comparative example 7
The preparation of up-conversion: in 100mL round-bottomed flask, 10mL 0.1molL is sequentially added-1Rare-earth salts is water-soluble
Liquid (wherein yttrium salt: ytterbium salt: the molar ratio of erbium salt is 0.88:0.10:0.02), 7.5mL 0.1molL-1The water of trisodium citrate
Solution and 20mL 0.025molL-1Halogenated phosphates ethanol solution, stirs 30min at room temperature, obtains milky
Suspension.Then, 12mL 1molL is added dropwise into the milky suspension-1The aqueous solution of NaF, stirs 1h at room temperature.
Resulting suspension is transferred in 100mL hydrothermal reaction kettle, and 0.1molL is added-1NaOH aqueous solution section system pH=10,
Reaction 12h is stood in 180 DEG C of baking oven.After completion of the reaction, reaction system cooled to room temperature, centrifuge separation
(12000rpm, 10min) and with ethanol washing (three times), product obtains white powder, products therefrom in 60 DEG C of vacuum drying 6h
Scanning electron microscope (SEM) photograph as shown in fig. 7, the product obtained when pH value of reaction system is 10 is amorphous material.
Implementation method of the invention is explained in detail above in conjunction with embodiment, but the present invention is not limited to above-mentioned
Embodiment can also not depart from present inventive concept within the knowledge of one of ordinary skill in the art
Premise makes a variety of changes.
Claims (9)
1. a kind of rear-earth-doped NaYF of dendroid4The preparation method of up-conversion, it is characterised in that: in rare earth salt aqueous solution,
Anionic surfactant solution, cationic surfactant solution and NaF aqueous solution is added and is transferred to water after mixing evenly
In hot kettle, it is dilute to get hexagonal phase dendroid to carry out hydro-thermal reaction at a temperature of 160 DEG C~240 DEG C for regulation system pH value to 1~2
Soil doping NaYF4Up-conversion；
The anionic surfactant solution is trisodium citrate aqueous solution；
The cationic surfactant solution is halogenated phosphates ethanol solution；
The molar ratio of trisodium citrate and rare-earth salts is 0.5~1.5:1.0 in the citric acid three sodium solution；
The halogenated phosphates Chlorine in Solution is 0.40~1.0 for the molar ratio of cetyl pyridinium and rare-earth salts:
1.0；
The molar ratio of NaF and rare-earth salts is 12~18:1 in the NaF aqueous solution.
2. the rear-earth-doped NaYF of dendroid according to claim 14The preparation method of up-conversion, it is characterised in that:
The concentration of the aqueous solution of anionic surfactant is 0.07~0.20molL-1；
The cationic surfactant ethanol solution concentration is 0.02~0.05molL-1；
The solubility of NaF aqueous solution is 1.0~1.5molL-1；
The volume ratio of water and ethyl alcohol is 2~4:2 in system.
3. the rear-earth-doped NaYF of dendroid according to claim 1 or 24The preparation method of up-conversion, feature exist
In: it include yttrium salt, ytterbium salt, M1 salt and M2 salt in the rare-earth salt solution；Yttrium salt, ytterbium salt, M1 salt and M2 salt molar ratio be
(90-x-y): 10:x:y, 0≤x, y < 3,2≤x+y < 5；M1 salt and M2 salt are independently selected from erbium salt, thulium salt or holmium salt.
4. the rear-earth-doped NaYF of dendroid according to claim 34The preparation method of up-conversion, it is characterised in that:
The ytterbium salt is ytterbium chloride and/or ytterbium nitrate；
The yttrium salt is yttrium chloride and/or yttrium nitrate；
The erbium salt is erbium chloride and/or erbium nitrate；
The thulium salt is thulium chloride and/or thulium nitrate；
The holmium salt is holmium chloride and/or holmium nitrate.
5. the rear-earth-doped NaYF of dendroid according to claim 1 or 24The preparation method of up-conversion, feature exist
Be 8 in: time of the hydro-thermal reaction~for 24 hours.
6. a kind of rear-earth-doped NaYF of dendroid4The application of up-conversion, it is characterised in that: by any one of Claims 1 to 5
The rear-earth-doped NaYF of dendroid of the preparation method preparation4Up-conversion is as fluorescent functional applying filler in preparing fluorescence
Laminated film.
7. the rear-earth-doped NaYF of dendroid according to claim 64The application of up-conversion, it is characterised in that: dendroid
Rear-earth-doped NaYF4Up-conversion is blended with PVA, and dissolution prepares fluorescence PVA film by the tape casting.
8. the rear-earth-doped NaYF of dendroid according to claim 74The application of up-conversion, it is characterised in that: by branch
The rare earth ion doped NaYF of shape4Up-conversion and PVA (0.1~4) in mass ratio: 100 mixed dissolutions, cooling, tape casting,
To obtain the final product.
9. the rear-earth-doped NaYF of dendroid according to claim 84The application of up-conversion, it is characterised in that: be cast into
Laminated film obtained by type is with a thickness of 0.06mm~0.2mm.
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| CN101699636A (en) * | 2009-10-22 | 2010-04-28 | 厦门大学 | Preparation method of fluorescent film capable of improving conversion efficiency of solar cell |
| CN105694883A (en) * | 2016-03-29 | 2016-06-22 | 沈阳化工大学 | Method for controlling particle size and shape of nano powder |
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