CN110437823A - The preparation and the application in package anti-counterfeiting of a kind of zinc oxide europium-doped luminous material - Google Patents
The preparation and the application in package anti-counterfeiting of a kind of zinc oxide europium-doped luminous material Download PDFInfo
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- CN110437823A CN110437823A CN201910748121.7A CN201910748121A CN110437823A CN 110437823 A CN110437823 A CN 110437823A CN 201910748121 A CN201910748121 A CN 201910748121A CN 110437823 A CN110437823 A CN 110437823A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7729—Chalcogenides
- C09K11/773—Chalcogenides with zinc or cadmium
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Abstract
The preparation and the application in package anti-counterfeiting of a kind of zinc oxide europium-doped luminous material, belong to anti-fake material technical field.Weigh Zn (CH3COOH)2It is mixed with europium nitrate solution, will weigh after object is placed in reaction kettle, ethyl alcohol and urea is added, then carries out uniform stirring 30 minutes；The mixed solution of above-mentioned preparation is placed in the Muffle furnace for setting temperature, 250 DEG C of constant temperature are closed after keeping 3h, it is taken out after restoring etc. entire reaction system natural cooling to room temperature, it is centrifuged after taking out sample, and deionized water and ethanol washing are used respectively, then it is dried, obtains powdered zinc oxide europium-doped nano material i.e. ZnO:Eu fluorescent material sample.ZnO:Eu nano material of the invention specific wavelength excitation under have issue visible spectrum band the characteristics of luminescence, and have good physicochemical property, can be used for pack it is anti-fake in.
Description
Technical field
The present invention relates to a kind of preparation method of zinc oxide europium-doped luminous material and the applications in package anti-counterfeiting field.Belong to
In field of nano-luminescent material.
Background technique
ZnO material has important structure feature, such as the influence of quantum confinement, dimensional effect, skin effect etc..This makes it
Have huge difference in the physical property of size, physical property and common materials.Zinc oxide material can be widely used for finely
Equipment, coloring agent, industrial material, chemical material etc..The particle of this material has photoelectric characteristic not available for traditional material,
Application performance of the zinc oxide in light and electricity can be obviously improved.Nano zine oxide is a kind of function semiconductor, is had been widely used for
Investigation of materials.It is highly valued especially as the material of blue light and ultraviolet photoelectron device.Currently, how research is in nanometer
There is the zinc oxide semiconductor material of excellent properties to be very important for preparation on scale, it is equally important that there are also the lifes of zinc oxide
Long and crystalline arrangement, this makes it possible the preparation and high efficiency of zno-based.
The electronic structure of rare earth element is very special, enough usable spectrums can be generated, so it is as luminescent material
Words, can almost cover all light emitting regions.Europium (Eu3+) it is a kind of important rare earth doped element of feux rouges.Trivalent rare earth from
The interior lattice of sub- europium ion incorporation nano zine oxide semiconductor, can generate new physics and chemical property.Due to interstitial impurity from
The ZnO band gap of son is larger, meets Eu3+It can be observed with the radiation phenomenon of red band.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of zinc oxide europium-doped luminous material and in package anti-counterfeiting
Application.
A kind of preparation method of zinc oxide europium-doped nano material, which comprises the following steps:
(1) europium nitrate solution, preferred concentration 0.05-0.2mmol/ml are prepared；
Weigh Eu2O3(purity: 99.9%) being mixed with deionized water, and in stirring while HNO is added dropwise3, it is heated to crystallizing
Afterwards, deionized water is added；
(2) Zn (CH is weighed3COOH)2It (purity: 99.9%) is mixed with the europium nitrate solution of step (1), object will be weighed
After being placed in reaction kettle, ethyl alcohol and urea is added, then carries out uniform stirring 30 minutes；The mixed solution of above-mentioned preparation is put
It is placed in the Muffle furnace for setting temperature, 250 DEG C of constant temperature are closed after keeping 3h, and entire reaction system natural cooling is waited to restore to room
It takes out after temperature, is centrifuged after taking out sample, and use deionized water and ethanol washing respectively, be then dried, obtain powder
Shape zinc oxide europium-doped nano material, that is, ZnO:Eu fluorescent material sample.
Every 8ml europium nitrate aqueous solution corresponds to 4ml ethyl alcohol and 0.0333mol urea.
Resulting materials, Eu3+Into nano-ZnO lattice without changing its original form, retain hexagonal wurtzite structure, sample
Size is in Nano grade.
ZnO:Eu nano material of the invention has the characteristics of luminescence for issuing visible spectrum band under specific wavelength excitation, and
With good physicochemical property, can be used for packing it is anti-fake in, resulting materials are entrained in glue, coating on the surface of the material or
Directly doping in the material, under dark room conditions, uses excitation wavelength to be irradiated for the light of 365nm, can significantly find,
ZnO:Eu nano material is mixed, there is apparent optical property.
Detailed description of the invention
Fig. 1 is the XRD spectrum of gained ZnO:Eu nano material sample after 250 DEG C of heat treatments in the embodiment of the present invention 1, wherein
The doping concentration of Eu is respectively 0%, 1%, 2%, 4%, 6%；Abscissa represents 2 θ of the angle of diffraction in figure, and unit is degree, ordinate
For diffraction relative intensity.
Fig. 2 is the scanning electron microscopy of gained ZnO:Eu nano material sample after 250 DEG C of heat treatments in the embodiment of the present invention 1
Mirror (SEM) photo, europium doping concentration are 4%.
Fig. 3 is the luminescence generated by light light of gained ZnO:Eu nano material sample after 250 DEG C of heat treatments in the embodiment of the present invention 1
Spectrum, excitation wavelength 360nm；Abscissa is wavelength of transmitted light, unit nm in figure；Ordinate is transmitting relative intensity, unit
For a.u..
Fig. 4 is the x-ray photoelectron of gained ZnO:Eu nano material sample after 250 DEG C of heat treatments in the embodiment of the present invention 1
Power spectrum.
Fig. 5 is to carry out in gained ZnO:Eu nano material sample incorporation glue after 250 DEG C of heat treatments in the embodiment of the present invention 1
The photo that optical anti-counterfeiting is probed into, left side are normal light irradiation, and right side is the ultraviolet light under excitation wavelength is 365nm.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1
(1) Eu is weighed2O3(purity: 99.9%) being mixed with deionized water, and in stirring while dense HNO is slowly added dropwise3
(purity: 99.9%), after being heated to crystallization, deionized water is added, prepares the europium nitrate solution of 0.1mmol/ml；It weighs a certain amount of
Zn (CH3COOH)2(purity: 99.9%) and 8ml europium nitrate, will weigh after object is placed in reaction kettle, be added 4ml ethyl alcohol with
Then 0.0333mol urea carries out uniform stirring 30 minutes；The mixed solution of above-mentioned preparation is placed in the horse for setting temperature
Not in furnace, 250 DEG C of constant temperature are closed after keeping 3h, are taken out after waiting entire reaction system natural cooling to restore to room temperature, take out sample
After be centrifuged, and respectively use deionized water and ethanol washing, be then dried, obtain powdered zinc oxide europium-doped nano material
Material is ZnO:Eu fluorescent material sample.Then ZnO:Eu nano material obtained is mixed in glue, it is anti-carries out preliminary optics
Puppet is probed into.
(2) Fig. 1 is the XRD spectrum of gained ZnO:Eu nano material sample after 250 DEG C of heat treatments, wherein the doping concentration of Eu
Respectively 0%, 1%, 2%, 4%, 6%.As seen from the figure, the XRD spectrum of ZnO:Eu nano particle does not show Eu2O3With remove ZnO
Except any impurity peak, this show ZnO:Eu have high phase purity.
(3) Fig. 2 is scanning electron microscope (SEM) photo of gained ZnO:Eu nano material sample after 250 DEG C of heat treatments,
Wherein europium doping concentration is 4%, it can be seen that Eu3+Into nano-ZnO lattice without changing its original form, retain six side's fibre zinc
Mine structure, sample size is in Nano grade.
(4) Fig. 3 is the photoluminescence spectra of gained ZnO:Eu nano material sample after 250 DEG C of heat treatments, and excitation wavelength is
360nm；All ZnO:Eu3+Sample all shows two spikes at 595nm and 617nm, respectively due to Eu3+Ion5D0
-7F1With5D0-7F2Transition.It can be found that sample is with Eu3+The peak value of the increase of doping concentration, red emission peak is gradually increased,
Photoluminescence intensity increases, and when doping concentration is 4%, reaches highest；However, peak value is opened when doping concentration increases to 6%
Begin to reduce, photoluminescence intensity starts the phenomenon that downward trend is presented, generates fluorescent quenching, and photoluminescence intensity is with doping concentration
Increase and weakened, this may be since the surface nature of nano particle affects its luminescent properties.In addition to similar Eu3+From
Outside sub- doping concentration dependence and broader transmitting range, the best 4% doping concentration sample prepared at 250 DEG C is in 617nm
The PL intensity peak at place is clearly more powerful.
(5) Fig. 4 be 250 DEG C heat treatment after gained ZnO:Eu nano material sample x-ray photoelectron spectroscopy, Cong Tuke with
Find out, the high-resolution in the XPS spectrum of the ZnO sample of 4%Eu doping, at the peak Eu 3d of 1120-1180eV energy area
Four peaks of Eu are measured in spectrum.Eu 3d5/2And 3d3/2Peak respectively appears in 1134.8ev and 1162.2eV, it means that Eu3+
With the presence of O chemical bonding.This shows Eu3+Oxidation state be trivalent.
(6) Fig. 5 mixes the photograph for carrying out optical anti-counterfeiting in glue and probing into for gained ZnO:Eu nano material after 250 DEG C of heat treatments
Piece.It can be seen from the figure that mixing the glue of ZnO:Eu nano material, not any luminous effect under normal light-illuminating
Fruit (Fig. 5 on the left of), correspondingly be then to use excitation wavelength to be irradiated for the light of 365nm under dark room conditions, can be with
Apparent discovery mixes the glue of ZnO:Eu nano material with this condition, has apparent optical property (on the right side of Fig. 5).
Claims (7)
1. a kind of preparation method of zinc oxide europium-doped nano material, which comprises the following steps:
(1) europium nitrate solution is prepared；
(2) Zn (CH is weighed3COOH)2(purity: 99.9%) being mixed with the europium nitrate solution of step (1), and object placement will be weighed
After in reaction kettle, ethyl alcohol and urea is added, then carries out uniform stirring 30 minutes；The mixed solution of above-mentioned preparation is placed in
It sets in the Muffle furnace of temperature, 250 DEG C of constant temperature are closed after keeping 3h, and entire reaction system natural cooling is waited to restore to room temperature
It takes out, is centrifuged after taking out sample, and use deionized water and ethanol washing respectively, be then dried, obtain powdered oxygen
Change zinc europium-doped nano material, that is, ZnO:Eu fluorescent material sample.
2. a kind of preparation method of zinc oxide europium-doped nano material described in accordance with the claim 1, which is characterized in that step (1)
It prepares europium nitrate solution: weighing Eu2O3It is mixed with deionized water, in stirring while HNO is added dropwise3, after being heated to crystallization, add
Enter deionized water.
3. a kind of preparation method of zinc oxide europium-doped nano material described in accordance with the claim 1, which is characterized in that europium nitrate is molten
Liquid concentration 0.05-0.2mmol/ml.
4. a kind of preparation method of zinc oxide europium-doped nano material described in accordance with the claim 1, which is characterized in that every 8ml nitre
Sour europium aqueous solution corresponds to 4ml ethyl alcohol and 0.0333mol urea.
5. according to the zinc oxide europium-doped nano material of the described in any item method preparations of claim 1-4.
6. according to the doped zinc oxide europium applications to nanostructures of the described in any item method preparations of claim 1-4, for packing
It is anti-fake in.
7. according to the application of claim 6, which is characterized in that ZnO:Eu is material doped in glue, and coating is on the surface of the material
Or directly doping in the material, under dark room conditions, uses excitation wavelength to be irradiated for the light of 365nm, incorporation ZnO:Eu receives
Rice material, has apparent optical property.
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| CN201910748121.7A CN110437823A (en) | 2019-08-13 | 2019-08-13 | The preparation and the application in package anti-counterfeiting of a kind of zinc oxide europium-doped luminous material |
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| CN201910748121.7A CN110437823A (en) | 2019-08-13 | 2019-08-13 | The preparation and the application in package anti-counterfeiting of a kind of zinc oxide europium-doped luminous material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113203702A (en) * | 2021-04-15 | 2021-08-03 | 重庆科技学院 | Method for measuring content of aflatoxin B1 in alfalfa forage grass |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105293565A (en) * | 2015-10-16 | 2016-02-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparing method for light-color doping nanometer electro-conductive zinc oxide powder |
-
2019
- 2019-08-13 CN CN201910748121.7A patent/CN110437823A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105293565A (en) * | 2015-10-16 | 2016-02-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparing method for light-color doping nanometer electro-conductive zinc oxide powder |
Non-Patent Citations (2)
| Title |
|---|
| LI FUHUA: "Preparation, Photoluminescence and Photocatalytic Properties of ZnO:Eu3+ Nanocrystals", 《JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY》 * |
| 邹科: "ZnO纳米材料的铝、稀土掺杂及其光学和电学性能研究", 《中国博士学位论文全文数据库》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113203702A (en) * | 2021-04-15 | 2021-08-03 | 重庆科技学院 | Method for measuring content of aflatoxin B1 in alfalfa forage grass |
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