CN109735339A - A kind of multi-mode fluorescence composite material and its preparation method and application - Google Patents
A kind of multi-mode fluorescence composite material and its preparation method and application Download PDFInfo
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Abstract
The present invention is a kind of multi-mode fluorescence composite material and its preparation method and application.The chemical formula of the material is NaYxF4:Lny 3+/NaYwF4:Euz 3+；Wherein, Ln3+For Yb3+, Er3+And Tm3+In two kinds in three kinds of elements；The composite material is white powder, NaYxF4:Lny 3+For six square rod shapes, the length of six square rod shapes is 5-8 μm, and the diameter of the hexagon on top is 1-3 μm；NaYwF4:Euz 3+For spheric granules, the partial size of particle is 0.02~0.09 μm；NaYwF4:Euz 3+Particle is attached to NaYxF4:Lny 3+It surface and is centered around around it.The composite material that the present invention obtains can launch the light of different colours in near-infrared and ultraviolet lamp or both while under irradiating, and have good fluorescence purity.
Description
Technical field:
The invention belongs to luminescent material technical fields, and in particular to a kind of to have upper conversion and lower conversion luminous power simultaneously
Fluorescent material and preparation method thereof and Application in Anti-counterfeiting.
Background technique
In recent years, the counterfeit and shoddy goods to emerge one after another not only very disruptive civil order, or even the health of people made
At different degrees of injury.Therefore, the safe practice of many strike fake and forged phenomenons is just come into being.Wherein, fluorescence is anti-
Puppet is a kind of counterfeit protection measures being commonly used, and the fluorescent material of trivalent rare earth ions doping is ground by its series of advantages
The extensive concern for the person of studying carefully, such as excellent photostability, longer fluorescence lifetime, stable energy level and relatively narrow transmitting band etc..It is logical
Normal luminescence process is divided into up-conversion luminescence (absorb the photon of low energy and release the photon of high-energy) and in contrast lower turn
Change photoreduction process.It is understood that Ln3+The NaYF of doping4It has been considered to be most effective upper conversion and one of lower transition material,
NaYF4The relatively low (~370cm of maximum phonon energy-1), chemical stability is high, and refractive index is low, greater band gap (~4.4eV) and
It can be Ln3+Suitable lattice sites are provided.
It is a kind of based on group of the lanthanides NaYF that Patent publication No has been the patent disclosure of 107641375 A of CN4Up-conversion luminescence oil
Ink, although having been achieved the effect that using the concealment of up-conversion luminescence anti-fake, the luminescent material of single-mode is only together
Defence line is protected, is still easy to be replicated counterfeit.
Although other also some research are reported about double mode fluorescence falsification preventing material, they mostly use complexity
Core-shell structure, preparation condition is comparatively laborious.
Summary of the invention
It is an object of the present invention to provide a kind of fluorescence NaY of multi-mode for deficiency present in current techniquesxF4:Lny 3 +/NaYwF4:Euz 3+Composite material and preparation method and Application in Anti-counterfeiting.Different from general multi-mode core-shell structure, this is compound
Material is simple composite deposition structure, i.e., many NaYwF4:Euz 3+Spheric granules random deposition is distributed in NaYxF4:Lny 3+Six
Square rod shape surface.The composite material can launch the light of different colours in the case where near-infrared and ultraviolet lamp or both irradiate simultaneously,
With good fluorescence purity.Using three kinds of colors of R-G-B as three primary colours, according to various combination different ratio it is available its
The fluorescence safety inks of his different colours is to be applied to anti-counterfeit field, the duplicate protection of its color diversity and multi-mode
Security performance will be greatly improved, a kind of high-level fluorescence falsification preventing material is become.
The present invention adopts the following technical scheme that:
A kind of multi-mode fluorescence composite material, the chemical formula of the material are NaYxF4:Lny 3+/NaYwF4:Euz 3+；Wherein, Ln3 +For Yb3+, Er3+And Tm3+In two kinds in three kinds of elements；
The composite material is white powder, NaYxF4:Lny 3+For six square rod shapes, the length of six square rod shapes is 5-8 μm, top
Hexagon diameter be 1-3 μm；NaYwF4:Euz 3+For spheric granules, the partial size of particle is 0.02~0.09 μm；NaYwF4:
Euz 3+Particle is attached to NaYxF4:Lny 3+It surface and is centered around around it；The value range of x is the value range of 0.6~0.9, y
It is 0.05~0.50 that the value range for being 0.1~0.4, w, which is the value range of 0.50~0.95, z,；NaYwF4:Euz 3+With
NaYxF4:Lny 3+Molar ratio be 1:2, wherein NaYwF4:Euz 3+With NaYxF4:Lny 3+Molal quantity contained with each
Lanthanide series total molar amount.
In the material, preferably are as follows: work as Ln3+For Yb3+And Er3+When, molar ratio Yb3+: Er3+=8:1~12:1,
NaYxF4:Lny 3+/NaYwF4:Euz 3+For NaYxF4:(Yb3+,Er3+)y/NaYwF4:Euz 3+, wherein x=0.70~0.90, y=
0.10~0.30, and x+y=1.0, w=0.50~0.95, z=0.05~0.50, and w+z=1.0；Work as Ln3+For Yb3+And Tm3+
When, molar ratio Yb3+: Tm3+=7:0.1~10:0.1, NaYxF4:Lny 3+/NaYwF4:Euz 3+For NaYxF4:(Yb3+,Tm3+)y/
NaYwF4:Euz 3+, wherein x=0.60~0.80, y=0.20~0.40, and x+y=1.0, w=0.50~0.95, z=0.05~
0.50, and w+z=1.0；Work as Ln3+For Er3+And Tm3+When, molar ratio Er3+: Tm3+=3:1~7:1, NaYxF4:Lny 3+/
NaYwF4:Euz 3+For NaYxF4:(Er3+,Tm3+)y/NaYwF4:Euz 3+, wherein x=0.80~0.90, y=0.10~0.20, and x+
Y=1.0, w=0.50~0.95, z=0.05~0.50, and w+z=1.0.
The NaYxF4:(Yb3+,Er3+)y/NaYwF4:Euz 3+Composite material is issued in the laser excitation that wavelength is 980nm
Green light out；NaYxF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+Composite material is issued in the case where wavelength is the laser excitation of 980nm
The light of blue；NaYxF4:(Er3+,Tm3+)y/NaYwF4:Euz 3+Composite material issues red in the case where wavelength is the laser excitation of 980nm
The light of color；These three composite materials all issue bright feux rouges under 365nm ultraviolet lamp photograph.
The preparation method of the multi-mode composite fluorescent material, including two steps:
Step 1, NaYxF4:Lny 3+Preparation process:
(1) it takes disodium EDTA to be dissolved in water, is made it completely dissolved under stirring, obtain solution A, solution A
Concentration range is 0.10-0.30mol.L-1；
(2) yttrium nitrate is taken, 2 kinds of rare earth nitrades are dissolved in water to form solution B, solution B is added in solution A, is obtained
Mixed solution has been arrived, 20~30min is stirred, the total concentration of nitrate is 0.05-0.2mol.L in solution B-1, 2 kinds of rare earth nitric acid
Proportion in salt is 3:1~10:0.1, and the volume ratio of solution A and solution B is solution A: solution B=2:5；The rare earth nitric acid
Salt is two kinds in ytterbium nitrate, erbium nitrate or thulium nitrate；
(3) it takes sodium fluoride aqueous solution to be add to the above mixed solution, 1~2h is stirred, by finally obtained mixed solution
It is transferred in reaction kettle, react 12 at 180~220 DEG C~for 24 hours, it is alternately washed with water and ethyl alcohol, just obtains NaYxF4:Lny 3+
Upconverting fluorescent material；The concentration range of sodium fluoride aqueous solution is 0.70-1.20mol.L-1, the volume of the solution and mixed solution
Than for 1:1；
Preferably, when rare earth nitrades are ytterbium nitrate and erbium nitrate in step (2), molar ratio is yttrium nitrate: ytterbium nitrate:
When erbium nitrate=78%:20%:2%, the NaY of acquisitionxF4:(Yb3+,Er3+)yFluorescent material swashs in the laser that wavelength is 980nm
Give the light for issuing green；When rare earth nitrades are ytterbium nitrate and thulium nitrate in step (2), molar ratio is yttrium nitrate: nitric acid
Ytterbium: when thulium nitrate=74.7%:25%:0.3%, the NaY of acquisitionxF4:(Yb3+,Tm3+)yFluorescent material is 980nm's in wavelength
The light of blue is issued under laser excitation；When rare earth nitrades are erbium nitrate and thulium nitrate in step (2), molar ratio is nitric acid
Yttrium: erbium nitrate: when thulium nitrate=88%:10%:2%, the NaY of acquisitionxF4:(Er3+,Tm3+)yFluorescent material is in wavelength
Red light is issued under 980nm laser excitation.
Preferably, the NaY that step (3) obtainsxF4:Lny 3+Upconverting fluorescent material can in the case where wavelength is 980nm laser excitation
To generate three kinds of colors of red, green, blue.
Step 2, NaYxF4:Lny 3+/NaYwF4:Euz 3+Preparation process:
(1) NaY is takenxF4:Lny 3+Up-conversion fluorescence particle is added in water and ethylene glycol mixed solution, obtains solution C, is stirred
20~30min is mixed, the concentration range of solution C is 2~8g.L-1；Volume ratio water: ethylene glycol=1:1；
(2) disodium ethylene diamine tetraacetate is taken, sodium fluoride, europium nitrate, yttrium nitrate is dissolved in water to form solution D, be added to
In solution C, then 80~120 DEG C, be heated to reflux under state and react 2~5h, finally gained is precipitated and is centrifuged, is washed, it is dry, obtain
To NaYxF4:Lny 3+/NaYwF4:Euz 3+Composite fluorescent material；
Wherein, molar ratio disodium ethylene diamine tetraacetate: sodium fluoride: europium nitrate: yttrium nitrate=1:10:0.2:0.8, ethylenediamine
The concentration range of tetraacethyl disodium solution is 0.05-0.15mol.L-1, the volume ratio of solution D and solution C is 1:2；
Preferably, the NaY that step (2) obtainsxF4:(Yb3+,Er3+)y/NaYwF4:Euz 3+, NaYxF4:(Yb3+,Tm3+)y/
NaYwF4:Euz 3+, NaYxF4:(Er3+,Tm3+)y/NaYwF4:Euz 3+Three kinds of composite fluorescent materials are issued in the ultraviolet light irradiation of 365nm
Bright feux rouges out, the NaY in the case where wavelength is the laser excitation of 980nmxF4:(Yb3+,Er3+)y/NaYwF4:Euz 3+It can issue green
The light of color, the NaY in the case where wavelength is the laser excitation of 980nmxF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+The light of blue can be issued,
The NaY in the case where wavelength is the laser excitation of 980nmxF4:(Er3+,Tm3+)y/NaYwF4:Euz 3+Red light can be issued.
The application of the multi-mode fluorescence composite material is used for encrypted print.
The encrypted print includes the following steps: NaYxF4:(Yb3+,Er3+)y/NaYwF4:Euz 3+, NaYxF4:(Yb3 +,Tm3+)y/NaYwF4:Euz 3+, NaYxF4:(Er3+,Tm3+)y/NaYwF4:Euz 3+Three kinds of composite fluorescent materials are dissolved in N, N- bis- respectively
In methylformamide (DMF) solvent, concentration is 0.0003~0.03g.mL-1；Then by NaYxF4:(Yb3+,Er3+)y/
NaYwF4:Euz 3+Solution as green ink, by NaYxF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+Solution as blue ink,
By NaYxF4:(Er3+,Tm3+)y/NaYwF4:Euz 3+Solution is injected separately into three print cartridges of ink-jet printer as red ink
In, it is printed.
The decryption method of the encrypted print, including the following two kinds mode:
Method one shows true color with the material for the laser irradiation encrypted print that wavelength is 980nm；
Alternatively, method two, the ultraviolet light irradiation for being 365nm with wavelength, printing content are shown in red.
Substantive distinguishing features of the invention are as follows:
The present invention is to be prepared for NaYxF4:Lny 3+/NaYwF4:Euz 3+Composite material, the composite material are different from general bimodulus
The core-shell structure of formula material, its structure are NaYwF4:Euz 3+Spheric granules is deposited on NaYxF4:Lny 3+The surface of six square rod shapes
And it is centered around around it, and the simple composite material of this structure is provided simultaneously with conversion and lower conversion luminous power.Preparation side
In method, by being heated to reflux 100 DEG C for NaYxF4:Lny 3+And NaYwF4:Euz 3+It is connected in the same structure.
The invention has the benefit that
1, the present invention is a kind of luminescent composite of multi-mode, has simple deposited complex structures.By adulterating not
Congener rare earth ion and the proportion for adjusting them, and by the method being simply heated to reflux by up-conversion luminescence and lower conversion
It shines and cleverly connects together, the composite material is enable to issue three kinds of red, green, blue in the case where wavelength is 980nm laser excitation
The light of color issues red light in the case where wavelength is the ultraviolet light irradiation of 365nm.
2, by being dispersed in DMF solution, using red, green, blue as three primary colours, the fluorescent ink of different colours has been adjusted out
Water, the duplicate protection with property rich in color and multi-mode will be for realizing high-caliber fluorescence falsification preventing.
Detailed description of the invention
Fig. 1 is NaY prepared by embodiment 2xF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+, NaYxF4:(Yb3+,Tm3+)y,
NaYwF4:Euz 3+XRD characterization figure, cubic phase NaYF4Standard x RD schemes (JCPDS NO.77-2042) and hexagonal phase NaYF4Standard
XRD diagram (JCPDS NO.28-1192)；
Fig. 2 is the NaY that embodiment 2 is preparedxF4:(Yb3+,Tm3+)yEnergy dispersion X-ray (EDAX) spectrogram；
Fig. 3 is the NaY that embodiment 2 is preparedxF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+Energy dispersion X-ray
(EDAX) spectrogram；
Fig. 4 is NaY prepared by embodiment 2xF4:(Yb3+,Tm3+)yThe shape appearance figure characterized under scanning electron microscope；
Fig. 5 is NaY prepared by embodiment 2xF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+The pattern characterized under scanning electron microscope
Figure；
Fig. 6 is NaY prepared by embodiment 1xF4:(Yb3+,Er3+)y/NaYwF4:Euz 3+In the laser excitation that wavelength is 980nm
Under fluorescence spectra；
Fig. 7 is NaY prepared by embodiment 2xF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+In the laser excitation that wavelength is 980nm
Under fluorescence spectra；
Fig. 8 is NaY prepared by embodiment 3xF4:(Er3+,Tm3+)y/NaYwF4:Euz 3+In the laser excitation that wavelength is 980nm
Under fluorescence spectra；
Fig. 9 is NaY prepared by embodiment 2xF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+Under the light excitation that wavelength is 393nm
Fluorescence spectra.
Figure 10 is the anti-counterfeiting ink figure that embodiment 4 is prepared based on multi-mode fluorescence composite material.Fig. 7 draw above is is matched
Fluorescence picture of the ink processed under 980nm laser irradiation；Horizontal stripe label below Fig. 7 corresponds to various colors fluorescent ink
One standard colour bar pattern；
Fluorogram of the prepared fluorescent ink of Figure 11 embodiment 4 under the ultraviolet light irradiation of 365nm.
Specific embodiment
Further detailed description is done to the present invention with reference to the accompanying drawings and embodiments, but embodiments of the present invention are unlimited
In this.
Embodiment 1
The embodiment of the present invention 1 is related to NaYxF4:(Yb3+,Er3+)y/NaYwF4:Euz 3+The preparation of composite material, specific steps
Are as follows: 1) it takes the disodium ethylene diamine tetraacetate of 2mmol to be dissolved in 8ml aqueous solution first, and is made it completely dissolved under ultrasonic treatment,
Then by the yttrium nitrate of total 2mmol, ytterbium nitrate and erbium nitrate (wherein molar content is yttrium nitrate: ytterbium nitrate: erbium nitrate=
It 78%:20%:2%) is dissolved in 20ml water, and is transferred in above-mentioned solution and obtains mixed solution, after stirring 30min, take
24mmol sodium fluoride is dissolved in 28ml water and is transferred in above-mentioned mixed solution, continues to stir 1h, transfers it to 100ml
In high-temperature high-pressure reaction kettle, 12h is reacted in 180 DEG C of baking oven, products therefrom is centrifuged (4500rpm/min, 5min), washing
(with alternately washing six times of water and ethyl alcohol), finally drying obtains NaY for 24 hours at 60 DEG CxF4:(Yb3+,Er3+)yMaterial is white
Solid powdery.
2) 0.1g NaY obtained above is takenxF4:(Yb3+,Er3+)ySolid powder is dissolved in the mixed of 10ml water and 10ml ethylene glycol
It closes in solution, ultrasonic 10min, stirs 30min；Then 1mmol disodium ethylene diamine tetraacetate is weighed, 0.80mmol yttrium nitrate,
0.20mmol europium nitrate, 10mmol sodium fluoride are dissolved in 10ml aqueous solution, and are transferred in above-mentioned mixed solution, then will be final
Resulting mixed solution is heated to reflux 3h at 100 DEG C, until there is precipitating to occur, by centrifugation (4500rpm/min, 5min),
It washs (water), is finally dried to obtain NaYxF4:(Yb3+,Er3+)y/NaYwF4:Euz 3+Composite material, same white solid powder
Shape.
Embodiment 2
The embodiment of the present invention 2 is related to NaYxF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+The preparation of composite material, specific steps
Are as follows: 1) it takes the disodium ethylene diamine tetraacetate of 2mmol to be dissolved in 8ml aqueous solution first, and is made it completely dissolved under ultrasonic treatment,
Then by the yttrium nitrate of total 2mmol, ytterbium nitrate, thulium nitrate (wherein molar content is yttrium nitrate: ytterbium nitrate: thulium nitrate=
It 74.7%:25%:0.3%) is dissolved in 20ml water, and is transferred in above-mentioned solution and obtains mixed solution, after stirring 30min,
It takes 24mmol sodium fluoride to be dissolved in 28ml water and is transferred in above-mentioned mixed solution, continue to stir 1h, transfer it to
In 100ml high-temperature high-pressure reaction kettle, react 12h in 180 DEG C of baking oven, by products therefrom centrifugation (4500rpm/min,
5min), washing (with alternately washing six times of water and ethyl alcohol), finally drying obtains NaY for 24 hours at 60 DEG CxF4:(Yb3+,Tm3+)yMaterial
Material, is white solid powder shape.2) 0.1g NaY obtained above is takenxF4:(Yb3+,Tm3+)ySolid powder be dissolved in 10ml water and
In the mixed solution of 10ml ethylene glycol, ultrasonic 10min stirs 30min；Then 1mmol disodium ethylene diamine tetraacetate is weighed,
0.80mmol yttrium nitrate, 0.20mmol europium nitrate, 10mmol sodium fluoride are dissolved in 10ml aqueous solution, and it is molten to be transferred to above-mentioned mixing
In liquid, final resulting mixed solution is then heated to reflux 3h at 100 DEG C, until there is precipitating to occur, passes through centrifugation
(4500rpm/min, 5min) washs (water), is finally dried to obtain NaYxF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+Composite material,
Same white solid powdery.
Embodiment 3
The embodiment of the present invention 3 is related to NaYxF4:(Er3+,Tm3+)y/NaYwF4:Euz 3+The preparation of composite material, specific steps
Are as follows: 1) it takes the disodium ethylene diamine tetraacetate of 2mmol to be dissolved in 8ml aqueous solution first, and is made it completely dissolved under ultrasonic treatment,
Then by the rare earth yttrium nitrate of total 2mmol, erbium nitrate, (wherein molar content is yttrium nitrate: erbium nitrate: nitric acid to thulium nitrate
Thulium=88%:10%:2%) it is dissolved in 20ml water, and be transferred in above-mentioned solution and obtain mixed solution, after stirring 30min,
It takes 24mmol sodium fluoride to be dissolved in 28ml water and is transferred in above-mentioned mixed solution, continue to stir 1h, transfer it to
In 100ml high-temperature high-pressure reaction kettle, react 12h in 180 DEG C of baking oven, by products therefrom centrifugation (4500rpm/min,
5min), washing (with alternately washing six times of water and ethyl alcohol), finally drying obtains NaY for 24 hours at 60 DEG CxF4:(Er3+,Tm3+)yMaterial
Material, is white solid powder shape.2) 0.1g NaY obtained above is takenxF4:(Er3+,Tm3+)ySolid powder be dissolved in 10ml water and
In the mixed solution of 10ml ethylene glycol, ultrasonic 10min stirs 30min；Then claim 1mmol disodium ethylene diamine tetraacetate,
0.80mmol yttrium nitrate, 0.20mmol europium nitrate, 10mmol sodium fluoride are dissolved in 10ml aqueous solution, and it is molten to be transferred to above-mentioned mixing
In liquid, final resulting mixed solution is then heated to reflux 3h at 100 DEG C, until there is precipitating to occur, passes through centrifugation
(4500rpm/min, 5min) washs (water), is finally dried to obtain NaYxF4:(Er3+,Tm3+)y/NaYwF4:Euz 3+Composite material,
Same white solid powdery.
Fig. 1 is NaY prepared by embodiment 2xF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+, NaYxF4:(Yb3+,Tm3+)y,
NaYwF4:Euz 3+XRD characterization figure, cubic phase NaYF4Standard x RD schemes (JCPDS NO.77-2042) and hexagonal phase NaYF4Standard
XRD diagram (JCPDS NO.28-1192), by XRD diagram, it is known that the NaY that we preparexF4:(Yb3+,Tm3+)yCrystalline form with
Hexagonal phase NaYF4Standard x RD figure is consistent, is hexagonal phase NaYF4, NaYwF4:Euz 3+Crystalline form and cubic phase NaYF4Standard x RD figure
It unanimously, is cubic phase NaYF4, and NaYxF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+It is the mixed phase of cubic phase and hexagonal phase.It is real
The XRD diagram applied before and after Material cladding prepared by example 1 and embodiment 3 is all identical as material XRD characterization prepared by embodiment 2.
Fig. 2 is the NaY that embodiment 2 is preparedxF4:(Yb3+,Tm3+)yEnergy dispersion X-ray (EDAX) spectrogram, from
Na, Y, F, Yb, the presence of Tm element can have been confirmed in figure.
Table 1 (see the table below) is the NaY that embodiment 2 is preparedxF4:(Yb3+,Tm3+)yEach element quality percentage
Number, what needs to be explained here is that due to the Elemental redistribution amount that can only obtain object surface layer by elemental analysis, so each element
Ratio and the ratio actually synthesized description, which are compared, can have certain deviation.
Table 1
| Element | F | Na | Y | Yb | Tm |
| Quality % | 40.30 | 16.30 | 29.92 | 1.01 | 12.47 |
Fig. 3 is the NaY that embodiment 2 is preparedxF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+Energy dispersion X-ray
(EDAX) spectrogram can confirm Na, Y, F, Yb, Tm, the presence of Eu element from figure.C, O element are instrument test itself
Element.
Table 2 (see the table below) is the NaY that embodiment 2 is preparedxF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+Each element
Mass percent, also need explanation here is Elemental redistribution due to can only obtain object surface layer by elemental analysis
Amount, so each element ratio and the ratio actually synthesized description, which are compared, can have certain deviation.
Table 2
| Element | C | O | F | Na | Y | Yb | Tm | Eu |
| Quality % | 20.48 | 5.17 | 36.81 | 12.89 | 19.20 | 4.64 | 0.08 | 0.74 |
Fig. 4 is NaY prepared by embodiment 2xF4:(Yb3+,Tm3+)yThe shape appearance figure characterized under scanning electron microscope, can from figure
NaY is seen with what is be apparentxF4:(Yb3+,Tm3+)yIt is six sides club shaped structure of uniform morphology.The length of six square rod shapes is 5-8 μ
M, the diameter of the hexagon on top are 1-3 μm.
Fig. 5 is NaY prepared by embodiment 2xF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+The pattern characterized under scanning electron microscope
Figure, it can be seen from the figure that the structure of the composite material is many NaYwF4:Euz 3+Spheric granules (partial size of particle be 0.02~
0.09 μm) it is deposited on NaYxF4:(Yb3+,Tm3+)ySurface and be centered around around it.It may be noted that NaYxF4:(Yb3+,Er3+)y/
NaYwF4:Euz 3+, NaYxF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+, NaYxF4:(Er3+,Tm3+)y/NaYwF4:Euz 3+Three kinds of materials
It is homologue, so in compound front and back appearance structure all having the same, so only providing here a kind of as reference.
Fig. 6 is the NaY that embodiment 1 is preparedxF4:(Yb3+,Er3+)y/NaYwF4:Euz 3+Composite fluorescent material is in wavelength
For the fluorescence spectra under 980nm laser excitation, as can be seen from the figure in the case where wavelength is 980nm laser excitation, NaYxF4:
(Yb3+,Er3+)y/NaYwF4:Euz 3+The wave band launched is mainly in the green fluorescence of 544nm.
Fig. 7 is the NaY that embodiment 2 is preparedxF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+Composite fluorescent material is in wavelength
For the fluorescence spectra under 980nm laser excitation, as can be seen from the figure in the case where wavelength is 980nm laser excitation, NaYxF4:
(Yb3+,Tm3+)y/NaYwF4:Euz 3+Emission band is mainly in the blue-fluorescence of 476nm.
Fig. 8 is the NaY that embodiment 3 is preparedxF4:(Er3+,Tm3+)y/NaYwF4:Euz 3+Composite fluorescent material is in wavelength
For the fluorescence spectra under 980nm laser excitation, as can be seen from the figure in the case where wavelength is 980nm laser excitation, NaYxF4:
(Er3+,Tm3+)y/NaYwF4:Euz 3+Emission band is mainly in the red fluorescence of 659nm wave band.
Fig. 9 is NaY prepared by embodiment 2xF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+Fluorescence spectrum under 393nm excitation
Figure, as can be seen from the figure under 393nm laser excitation, NaYxF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+Emission band exists
The red band of 616nm and 651nm.Since other two kinds of materials issue feux rouges and NaY at 393nmxF4:(Yb3+,Tm3+)y/
NaYwF4:Euz 3+Fluorescence spectrum having the same, so only listing one kind here.
Embodiment 4
The present embodiment 4 is related to the preparation of multi-mode composite fluorescent material multicolor fluorescence ink, specific as follows: 1) to take first
0.1g NaYxF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+Composite material is dissolved in 10ml DMF solution, be configured to be in wavelength
The ink of blue-fluorescence is issued under 980nm laser irradiation；Take 0.1g NaYxF4:(Er3+,Tm3+)y/NaYwF4:Euz 3+Composite material
It is dissolved in 10ml DMF solution, is configured to issue the ink of red fluorescence in the case where wavelength is 980nm laser excitation；Take 0.01g
NaYxF4:(Yb3+,Er3+)y/NaYwF4:Euz 3+Composite material is dissolved in 10ml DMF solution, is configured to issue in 980nm irradiation
The ink of green fluorescence out.2) by the above-mentioned fluorescent ink for issuing three kinds of colors of red, green, blue in the case where wavelength is 980nm laser excitation
Water has been adjusted to issue powder, purple, blueness, Huang Si kind color in the case where wavelength is 980nm laser excitation by certain combination certain proportion
Fluorescent ink.Specifically when volume ratio is red: pink colour is obtained when indigo plant=2:1, when indigo plant: purple is obtained when red=2:1, when green: blue=
Cyan is obtained when 1:4, when green: obtaining yellow when red=1:4.This seven kinds of fluorescent inks issue under the ultraviolet light irradiation of 365nm
Bright red.
Figure 10 is the anti-counterfeiting ink figure that embodiment 4 is prepared based on multi-mode fluorescence composite material.Fig. 7 draw above is is matched
Fluorescence picture of the ink processed under 980nm laser irradiation；Horizontal stripe label below Fig. 7 corresponds to various colors fluorescent ink
One standard colour bar pattern, as we can see from the figure with the red, green, blues of bright colors, Huang, powder, blueness, purple seven kinds of colors fluorescence
Ink, by comparing with standard colour bar pattern, which shows good fluorescence purity.
Fluorogram of the prepared fluorescent ink of Figure 11 embodiment 4 in the case where wavelength is the ultraviolet light irradiation of 365nm, can from figure
To find out, this seven kinds of fluorescent inks issue bright red in the case where wavelength is the ultraviolet light irradiation of 365nm.
By NaYxF4:(Yb3+,Er3+)y/NaYwF4:Euz 3+, NaYxF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+, NaYxF4:
(Er3+,Tm3+)y/NaYwF4:Euz 3+Three kinds of composite fluorescent materials are dissolved in respectively in n,N-Dimethylformamide (DMF) solvent, so
Afterwards by NaYxF4:(Yb3+,Er3+)y/NaYwF4:Euz 3+Solution as green ink, by NaYxF4:(Yb3+,Tm3+)y/NaYwF4:
Euz 3+Solution is as blue ink, by NaYxF4:(Er3+,Tm3+)y/NaYwF4:Euz 3+For solution as red ink, we can be with
The three primary colors fluorescent ink that will be prepared, is injected into the correspondence print cartridge of common ink printer, according to printing content, beats
Print off the complex pattern with different colours, the pattern be in its natural state it is colourless, when wavelength be 980nm laser swash
It gives, it can be seen that different colors, and be displayed in red in the case where wavelength is the ultraviolet light irradiation of 365nm, so passing through the fluorescence
Ink can prepare the safe-guarding and anti-counterfeiting pattern with highly concealed type, and upper conversion is converted luminous power and provided into this ink with lower
Duplicate protection, so being difficult to be replicated by the security pattern that it is prepared, so as to realize high-caliber fluorescence falsification preventing.
The above is only exemplary embodiment of the present invention, are not intended to restrict the invention, all in principle of the present invention
The equivalent replacement and further improvement done, should all be included in the protection scope of the present invention.
Unaccomplished matter of the present invention is well-known technique.
Claims (8)
1. a kind of multi-mode fluorescence composite material, it is characterized in that the chemical formula of the material is NaYxF4:Lny 3+/ NaYwF4:Euz 3+；
Wherein, Ln3+For Yb3+, Er3+And Tm3+In two kinds in three kinds of elements；
The composite material is white powder, NaYxF4:Lny 3+For six square rod shapes, the length of six square rod shapes is 5-8 μm, the six of top
The diameter of side shape is 1-3 μm；NaYwF4:Euz 3+For spheric granules, the partial size of particle is 0.02 ~ 0.09 μm；NaYwF4:Euz 3+?
Grain is attached to NaYxF4:Lny 3+It surface and is centered around around it；The value range of x be the value range of 0.6 ~ 0.9, y be 0.1 ~
0.4, w value range is that the value range of 0.50 ~ 0.95, z is 0.05 ~ 0.50；NaYwF4:Euz 3+With NaYxF4:Lny 3+Rub
You are than being 1:2, wherein NaYwF4:Euz 3+With NaYxF4:Lny 3+The lanthanide series that is contained with each of molal quantity it is total
Molar amount.
2. multi-mode fluorescence composite material as described in claim 1, it is characterized in that working as Ln3+For Yb3+And Er3+When, molar ratio is
Yb3+: Er3+=8:1 ~ 12:1, NaYxF4:Lny 3+/ NaYwF4:Euz 3+ For NaYxF4:(Yb3+,Er3+)y/ NaYwF4:Euz 3+, wherein
X=0.70 ~ 0.90, y=0.10 ~ 0.30, and x+y=1.0, w=0.50 ~ 0.95, z=0.05 ~ 0.50, and w+z=1.0；Work as Ln3+For
Yb3+And Tm3+When, molar ratio Yb3+: Tm3+=7:0.1 ~ 10:0.1, NaYxF4:Lny 3+/ NaYwF4:Euz 3+For NaYxF4:(Yb3 +,Tm3+)y/ NaYwF4:Euz 3+, wherein x=0.60 ~ 0.80, y=0.20 ~ 0.40, and x+y=1.0, w=0.50 ~ 0.95, z=0.05 ~
0.50, and w+z=1.0；Work as Ln3+For Er3+And Tm3+When, molar ratio Er3+: Tm3+=3:1 ~ 7:1, NaYxF4:Lny 3+/ NaYwF4:
Euz 3+For NaYxF4:(Er3+,Tm3+)y/ NaYwF4:Euz 3+, wherein x=0.80 ~ 0.90, y=0.10 ~ 0.20, and x+y=1.0, w=
0.50 ~ 0.95, z=0.05 ~ 0.50, and w+z=1.0.
3. multi-mode fluorescence composite material as claimed in claim 2, it is characterized in that the NaYxF4:(Yb3+,Er3+)y/
NaYwF4:Euz 3+Composite material issues the light of green in the case where wavelength is the laser excitation of 980 nm；NaYxF4:(Yb3+,Tm3+)y/
NaYwF4:Euz 3+Composite material issues the light of blue in the case where wavelength is the laser excitation of 980 nm；NaYxF4:(Er3+,Tm3+)y/
NaYwF4:Euz 3+Composite material issues red light in the case where wavelength is the laser excitation of 980 nm；These three composite materials are in wavelength
Bright feux rouges is all issued under shining for 365 nm ultraviolet lamps.
4. the preparation method of multi-mode composite fluorescent material as described in claim 1, it is characterized in that including the following steps:
Step 1, NaYxF4:Lny 3+Preparation process:
(1) it takes disodium EDTA to be dissolved in water, is made it completely dissolved under stirring, obtain solution A, solution A concentration
Range is 0.10-0.30 mol.L-1；
(2) yttrium nitrate is taken, 2 kinds of rare earth nitrades are dissolved in water to form solution B, solution B is added in solution A, is obtained
Mixed solution stirs 20 ~ 30 min, and the total concentration of nitrate is 0.05-0.2 mol in solution B.L-1, in 2 kinds of rare earth nitrades
Proportion be 3:1 ~ 10:0.1, the volume ratio of solution A and solution B is solution A: solution B=2:5；The rare earth nitrades are nitre
Two kinds in sour ytterbium, erbium nitrate or thulium nitrate；
(3) it takes sodium fluoride aqueous solution to be add to the above mixed solution, stirs 1 ~ 2 h, finally obtained mixed solution is shifted
Into reaction kettle, 12 ~ 24 h are reacted at 180 ~ 220 DEG C, are alternately washed with water and ethyl alcohol, are just obtained NaYxF4:Lny 3+It is upper to turn
Change fluorescent material；The concentration range of sodium fluoride aqueous solution is 0.70-1.20 mol.L-1, the volume ratio of the solution and mixed solution
For 1:1；
Step 2, NaYxF4:Lny 3+/ NaYwF4:Euz 3+Preparation process:
(1) NaY is takenxF4:Lny 3+Up-conversion fluorescence particle is added in water and ethylene glycol in mixed solution, obtains solution C, stirring
20 ~ 30min, the concentration range of solution C are 2 ~ 8g.L-1；Volume ratio water: ethylene glycol=1:1；
(2) disodium ethylene diamine tetraacetate is taken, sodium fluoride, europium nitrate, yttrium nitrate is dissolved in water to form solution D, is added to solution C
In, then 80 ~ 120 DEG C, be heated to reflux under state and react 2 ~ 5 h, finally gained is precipitated and is centrifuged, is washed, it is dry, obtain
NaYxF4:Lny 3+/ NaYwF4:Euz 3+Composite fluorescent material；
Wherein, molar ratio disodium ethylene diamine tetraacetate: sodium fluoride: europium nitrate: yttrium nitrate=1:10:0.2:0.8, ethylenediamine tetrem
The concentration range of acid disodium solution is 0.05-0.15 mol.L-1, the volume ratio of solution D and solution C is 1:2.
5. the preparation method of multi-mode composite fluorescent material as claimed in claim 4, it is characterized in that preferably, when step (2)
When middle rare earth nitrades are ytterbium nitrate and erbium nitrate, molar ratio is yttrium nitrate: ytterbium nitrate: erbium nitrate=78%:20%:2%, acquisition
NaYxF4:(Yb3+,Er3+)yFluorescent material；When rare earth nitrades are ytterbium nitrate and thulium nitrate in step (2), molar ratio is nitre
Sour yttrium: ytterbium nitrate: thulium nitrate=74.7%:25%:0.3%, the NaY of acquisitionxF4:(Yb3+,Tm3+)yFluorescent material；When in step (2)
When rare earth nitrades are erbium nitrate and thulium nitrate, molar ratio is yttrium nitrate: erbium nitrate: thulium nitrate=88%:10%:2%, acquisition
NaYxF4:(Er3+,Tm3+)yFluorescent material.
6. the application of multi-mode composite fluorescent material as described in claim 1, it is characterized in that being used for encrypted print.
7. the application of multi-mode composite fluorescent material as claimed in claim 6, it is characterized in that the encrypted print, including such as
Lower step: by NaYxF4:(Yb3+,Er3+)y/NaYwF4:Euz 3+, NaYxF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+, NaYxF4:(Er3 +,Tm3+)y/NaYwF4:Euz 3+Three kinds of composite fluorescent materials are dissolved in respectively in n,N-Dimethylformamide (DMF) solvent, and concentration is equal
For 0.0003 ~ 0.03 g.mL-1；Then by NaYxF4:(Yb3+,Er3+)y/NaYwF4:Euz 3+Solution as green ink, will
NaYxF4:(Yb3+,Tm3+)y/NaYwF4:Euz 3+Solution is as blue ink, by NaYxF4:(Er3+,Tm3+)y/NaYwF4:Euz 3+It is molten
Liquid is injected separately into three print cartridges of ink-jet printer, is printed as red ink.
8. the application of multi-mode composite fluorescent material as claimed in claim 7, it is characterized in that the solution of the encrypted print
Decryption method, including the following two kinds mode:
Method one, with the material for the laser irradiation encrypted print that wavelength is 980 nm, printing content shows true color；
Alternatively, method two, the ultraviolet light irradiation for being 365nm with wavelength, printing content are shown in red.
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