CN101271068B - Fluorescence intensity counter-rotative abrasion-proof bedaub-resistant fluorescence anti-counterfeiting method - Google Patents
Fluorescence intensity counter-rotative abrasion-proof bedaub-resistant fluorescence anti-counterfeiting method Download PDFInfo
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Abstract
The invention provides a double wavelength excited fluorescence intensity reverse type wear and stain resistant anti-counterfeiting method, which adopts a Yb<3+>X type rare earth nano material as the fluorescence anti-counterfeiting material (wherein, X is another rare earth element ion) to conduct fluorescence anti-counterfeiting according to the characteristic of the rare earth nano material that the fluorescence intensity reverse and the dynamic scope thereof are basically not changed after the material is worn or stained; the method includes the following steps: (1) laser light EX1 is selected to excite an X ion, so that the ion gives out strong short-wavelength fluorescence EM1 and weak long wavelength fluorescence EM2; 2) the fluorescence intensity ratio Alpha of the short wavelength fluorescence to the long wavelength fluorescence excited by the laser light EX1; (3) laser light EX2 is selected to excite the X ion, so that the ion gives out strong long wavelength fluorescence EM2 and weak short wavelength fluorescence EM1;(4) the fluorescence intensity reverse ratio Gamma of the long wavelength fluorescence and the short wavelength fluorescence excited by the laser light EX2; and (5) the reverse dynamic scope of the fluorescence intensity is calculated (Sigma=Gamma* Alpha).
Description
Technical field
The present invention relates to a kind of dual wavelength excited fluorescent method for anti-counterfeit, particularly, the present invention relates to the wear-resistant anti-fluorescence falsification preventing method of defiling of a kind of dual wavelength excited fluorescent intensity counter-rotative type, it adopts Yb
3+X type rare earth nano material is as the fluorescence falsification preventing material, and wherein X is another kind of rare earth element ion, utilizes the fluorescence intensity counter-rotating of this rare earth nano material and the constant substantially phenomenon of dynamic range of fluorescence intensity counter-rotating to carry out fluorescence falsification preventing.
Background technology
Along with expanding economy, fake and inferior commodities have become the countries in the world question of common concern as a kind of social phenomenon.A lot of in the world countries particularly some developed countries all drop into very big strength and develop various false proof new technologies, the false proof new technology of especially various high-tech.We have country's anti-counterfeiting technology commonly used: anti-forgery inks such as laser hologram, fluorescent material, water marked paper, fluorescent fiber, fluorescent ink, safety line, two-sided to anti-counterfeiting technologies such as seal, bar code, magnetic code, codes.What wherein attract people's attention is exactly the development and application of fluorescence falsification preventing technology, because the fluorescence falsification preventing technology has excellent safety and property easy to identify, it is very extensive that it is used aspect the high-tech anti-counterfeiting technology.The fluorescence falsification preventing The Application of Technology mainly contains Antiforge fluorescent ink and two aspects of fluorescence falsification preventing fiber now.Aspect these two, all obtained more general application and single wavelength fluorescent is false proof, for example, ultraviolet light induced visible fluorescence numeral on 100 yuans is exactly false proof means popular the most general after watermark, at aspects such as medicine, commodity important use is arranged also.
But it is false proof for single wavelength fluorescent, its principle is to be excited by a short wavelength light and launch the visible fluorescence of a long wave, the color of fluorescence is can not change to have good anti-counterfeiting performance, but along with the use of " false proof object ", fluorescence intensity is to have very big change.Reliably need allow some leeway in order to ensure technology, thereby the detection limit of fluorescence needs the little several times of maximum emission intensity than fluorescence; After so new a kind of false proof instrument is released, just give the adulterator,, can reach the luminous intensity of detection limit, make false proof reliability be affected though adulterator's fakement does not reach the luminous intensity of standard certified products with opportunity.
Summary of the invention
In order to address the above problem, we have proposed a kind of novel " the fluorescence intensity counter-rotative type is wear-resistant anti-defiling " fluorescence falsification preventing method, and this method adopts Yb
3+X type rare earth nano material is as the fluorescence falsification preventing material, wherein X is another kind of rare earth element ion, utilize the constant phenomenon of dynamic range of the fluorescence intensity counter-rotating of this rare earth nano material, by detecting normal fluorescence intensity ratio α, γ is compared in the fluorescence intensity counter-rotating, and the dynamic range Σ=γ * α of fluorescence intensity counter-rotating, differentiate the true and false of measured object, reach the purpose of fluorescence falsification preventing.
Particularly, the present invention relates to the wear-resistant anti-fluorescence falsification preventing method of defiling of a kind of dual wavelength excited fluorescent intensity counter-rotative type, this method adopts Yb
3+X type rare earth nano material is as the fluorescence falsification preventing material, and wherein X is another kind of rare earth element ion, utilizes the fluorescence intensity counter-rotating of this rare earth nano material and the constant substantially phenomenon of dynamic range of fluorescence intensity counter-rotating to carry out fluorescence falsification preventing, and described method comprises:
(1) selects for use exciting light EX1 to excite the X ion, make it send stronger short wavelength's fluorescence and more weak long wavelength's fluorescence;
(2) the short wavelength's fluorescence under detection exciting light EX1 excites and the fluorescence intensity ratio α of long wavelength's fluorescence;
(3) select for use exciting light EX2 to excite the X ion, make it send stronger long wavelength's fluorescence and more weak short wavelength's fluorescence;
(4) the long wavelength's fluorescence under detection exciting light EX2 excites compares γ with the fluorescence intensity counter-rotating of short wavelength's fluorescence;
(5) calculate dynamic range Σ=γ * α that fluorescence intensity is reversed.
That the inventive method detects is the dynamic range Σ of fluorescence intensity counter-rotating and fluorescence intensity counter-rotating, and the dynamic range Σ that fluorescence intensity is reversed is not only not with wearing and tearing and changes, but also not with defiling and change, environment does not change in time.Therefore can realize wear-resistant anti-fluorescence falsification preventing of defiling, and being provided with of detection limit can be very high very accurate,, thereby make the advance of fluorescence falsification preventing and reliability improve a lot with the standard certified products coupling of complete and false proof object.
Description of drawings
Fig. 1. nanophase oxyfluoride glass ceramic Er (0.5) Yb (3): the emission spectrum of the 378.5nm of FOV and 522.5nm absorption level.
Fig. 2. nanophase oxyfluoride glass ceramic Er (0.5): the emission spectrum of the 378.5nm of FOV and 522.5nm absorption level.
Fig. 3. nanophase oxyfluoride glass ceramic Er (0.5) Yb (3): the excitation spectrum of the 667.1nm of FOV and 543.7nm fluorescence.
Fig. 4. nanophase oxyfluoride glass ceramic Er (0.5): the excitation spectrum of the 543.7nm of FOV and 667.1nm fluorescence.
Fig. 5 .Yb
3+Er
3+Two system's fluorescence intensity counter-rotating synoptic diagram of mixing.
Fig. 6 .Yb
3+Tb
3+Two system's fluorescence intensity counter-rotating synoptic diagram of mixing.
Fig. 7 .Yb
3+Eu
3+Two system's fluorescence intensity counter-rotating synoptic diagram of mixing.
Embodiment
The present invention adopts Yb
3+X type rare earth nano material utilizes the fluorescence intensity counter-rotating of this rare earth nano material and the constant substantially phenomenon of dynamic range of fluorescence intensity counter-rotating to carry out fluorescence falsification preventing as the fluorescence falsification preventing material.Describe method of the present invention in detail below in conjunction with accompanying drawing and instantiation.
Yb
3+X type rare earth nano material
The Yb that the present invention uses
3+X type rare earth nano material belongs to the nano rare earth luminescent material.Present most of nano rare earth luminescent material is the rare earth nano powder body material, for example: Y
2O
3: Eu
3+, YVO
4: Ln, LaPO
4: Ln, Y
2SiO
5: Eu
3+, YAG (Y
3Al
5O
12): Ce
3+Deng.Rare earth nano material of the present invention adopts Yb
3+With the combination of other rare earth element ion, the special characteristics of luminescence of utilizing them to show in nano material is carried out fluorescence falsification preventing.Can be used for Yb of the present invention
3+The rare earth element of X type rare earth nano material except that Yb, comprises Er, Tb, Eu, Lu, La, Ce, Pr, Nd, Sm, Gd, Ho etc., wherein preferred combination comprise (Yb, Er), (Yb, Tb), (Yb, Eu) etc., preferred especially (Yb, Er) combination.
To can be used for Yb of the present invention
3+The nano material of X type rare earth nano material is not particularly limited.Can be used for nano material of the present invention and comprise various rare earth powder body materials and glass ceramic material, the glass ceramic material that wherein preferably contains the rare earth compound nano crystallite, more preferably rear-earth-doped alumina silicate glass that contains nano microcrystalline and oxyfluoride glass ceramic etc., preferred especially rare earth mixing with nano phase oxyfluoride glass ceramic.
Below, as Yb of the present invention
3+The representative embodiment of X type rare earth nano material is described nanophase oxyfluoride glass ceramic (FOV) in detail.
The nanophase oxyfluoride glass ceramic that uses among the present invention is to adopt Yuhu Wang and JunichiOhwaki at Appl.Phys.Lett., and disclosed method prepares among the Vol.63 (1993) 326.In this nanophase oxyfluoride glass ceramic material, the rare earth ion priority enrichment is in the fluoride microcrystal of about 20nm size, and described fluoride microcrystal forms in oxyfluoride glass by high-temperature heat treatment process.The transmitance of this nanophase oxyfluoride glass ceramic material does not have loss substantially, and is the same substantially with the parent oxyfluoride glass, only is the red shift a little that the absorption band edge of ultraviolet segment base matter has the scattering because of crystallite to cause; Though it contains the oxide of macro-energy phonon, as SiO
2, AlO
1.5, but infrared very high to visible non-linear luminescence efficiency.In a word, excellent chemical stability, physical strength and the high laser damage threshold of the existing general oxide of this nanophase oxyfluoride glass ceramic material have high non-linear luminescence efficiency again, and preparation also is easier to.
" fluorescence intensity counter-rotating " characteristic
Yb
3+X type rare earth nano material (X is another kind of rare earth element ion) can have peculiar " fluorescence intensity counter-rotating " phenomenon.Below with Yb
3+Er
3+Two nanophase oxyfluoride glass ceramics of mixing are example, explain this " fluorescence intensity counter-rotating " characteristic in detail.
Fig. 1 and Fig. 2 have shown Yb
3+Er
3+Admix Er altogether
3+Singly mix nanophase oxyfluoride glass ceramic Er (0.5) Yb (3): the Stokes emission spectrum of FOV and Er (0.5): FOV, they
4G
11/2The Stokes emission spectrum of energy level mainly contain (
2G
4F
2H)
9/2→
4I
15/2,
2H
11/2→
4I
15/2,
4S
3/2→
4I
15/2With
4F
9/2→
4I
15/2Several emission transition, spectrum spike length is respectively successively: 406.5nm, (522.5nm, 528.7nm) with (543.7nm, 550.2nm), (655.2nm, 667.1nm); Record theirs
2H
11/2The Stokes emission spectrum of energy level mainly contains
4S
3/2→
4I
15/2With
4F
9/2→
4I
15/2Two emission spectrum peaks, the spectrum spike long with
4G
11/2The Stokes emission spectrum of energy level is very approaching.
By Fig. 1 obviously can, for Er (0.5) Yb (3): FOV nanophase oxyfluoride glass ceramic, at the 522.1nm excited by visible light
2H
11/2Under the energy level situation, appearance be normal
4S
3/2Energy level 543.7nm green fluorescence strong and
4F
9/2The phenomenon that energy level 655.2nm red fluorescence is weak; And at the 378.6nm ultraviolet excitation
4G
11/2Under the energy level situation, appearance be unusual
4F
9/2The energy level red fluorescence strong and
4S
3/2The phenomenon that the energy level green fluorescence is weak, that is, and a kind of typical " red fluorescence intensity counter-rotating " phenomenon.
And from Fig. 2 as seen, for Er
3+Singly mix nanophase oxyfluoride glass ceramic Er (0.5): FOV, at the 522.1nm excited by visible light
2H
11/2Energy level and at the 378.6nm ultraviolet excitation
4G
11/2Under the energy level situation, appearance all be normal
4S
3/2Energy level 543.7nm green fluorescence strong and
4F
9/2There is not " fluorescence intensity counter-rotating " phenomenon fully in the phenomenon that energy level 655.2nm red fluorescence is weak.
Fig. 3 and Fig. 4 have shown Yb
3+Er
3+Admix Er altogether
3+Singly mix nanophase oxyfluoride glass ceramic Er (0.5) Yb (3): the excitation spectrum of FOV and Er (0.5): FOV.Er (0.5): the 543.7nm of FOV and 667.5nm fluorescence from
2G
7/2,
4G
9/2,
4G
11/2, (
2G
4F
2H)
9/2,
4F
3/2,
4F
5/2,
4F
7/2And
2H
11/2The ratio of the energy of acquisition that this several energy level absorbs is constant substantially.For Er (0.5) Yb (3): FOV sample, 543.7nm fluorescence be easy to from
4F
7/2With
2H
11/2These several energy levels obtain energy, and 667.5nm fluorescence be easy to from
4G
9/2With
4G
11/2These several energy levels obtain energy.
Although be reluctant to arrest in concrete theory, it is believed that Yb
3+Er
3+The Physical Mechanism of two " fluorescence intensity counter-rotating " characteristics of mixing the nanophase oxyfluoride glass ceramic is as follows.As shown in Figure 5, Er
3+Yb
3+Two systems of mixing exist
4G
11/2(Er
3+) →
4F
9/2(Er
3+),
2F
7/2(Yb
3+) →
2F
5/2(Yb
3+) and (
2G
4F
2H)
9/2(Er
3+) →
4F
9/2(Er
3+),
2F
7/2(Yb
3+) →
2F
5/2(Yb
3+) two intersect the NE BY ENERGY TRANSFER passages, the part population can be crossed
2H
11/2With
4S
3/2Energy level and directly transferring to
4F
9/2On the energy level.This just causes Er
3+Yb
3+Two systems of mixing are with respect to Er
3+Singly mix system and all some changes can be arranged.And, because the special nano microcrystalline structure of nanophase oxyfluoride glass ceramic, rare earth ion is concentrated in the crystallite of tens nanometers, distance R between the ion is acutely dwindled, making electric multipole interact improves greatly, even exchange interaction has further appearred, thereby great NE BY ENERGY TRANSFER appears, this just make
4G
11/2(Er
3+) →
4F
9/2(Er
3+),
2F
7/2(Yb
3+) →
2F
5/2(Yb
3+) and (
2G
4F
2H)
9/2(Er
3+) →
4F
9/2(Er
3+),
2F
7/2(Yb
3+) →
2F
5/2(Yb
3+) two rate of energy transfer that intersect the NE BY ENERGY TRANSFER passages violent raising is arranged, cause Er (0.5) Yb (3): " fluorescence intensity counter-rotating " characteristic appears in FOV nanophase oxyfluoride glass ceramic.
Other Yb
3+X type rare earth nano material also may have similarly " fluorescence intensity counter-rotating " characteristic.Fig. 6 and 7 has shown as Yb
3+Tb
3+Two system and Yb of mixing
3+Eu
3+Two fluorescence intensity counter-rotating synoptic diagram of mixing system.Shown in the arrow in Fig. 6 and 71 → 1 and 2 → 2, at Yb
3+Tb
3+Two mix in the system exist
5H
6(Tb
3+) →
5D
4(Tb
3+),
2F
7/2(Yb
3+) →
2F
5/2(Yb
3+) and
5D
1(Tb
3+) →
5D
4(Tb
3+),
2F
7/2(Yb
3+) →
2F
5/2(Yb
3+) two intersect the NE BY ENERGY TRANSFER passage, and at Yb
3+Eu
3+Two mix in the system exist
5H
7(Eu
3+) →
5D
1(Eu
3+),
2F
7/2(Yb
3+) →
2F
5/2(Yb
3+) and
5H
7(Eu
3+) →
5D
2(Eu
3+),
2F
7/2(Yb
3+) →
2F
5/2(Yb
3+) two intersect the NE BY ENERGY TRANSFER passage.Based on mechanism similar to the above, the rate of energy transfer of above-mentioned two intersection NE BY ENERGY TRANSFER passages has violent raising equally in these two kinds of nanophase oxyfluoride glass ceramics, cause Yb
3+Tb
3+Two mixing or Yb
3+Eu
3+The fluorescence intensity reverse speed characterisstic appears in two nanophase oxyfluoride glass ceramics of mixing.In fact, as long as there is strong intersection NE BY ENERGY TRANSFER passage, and the last energy level of this passage and following energy level all are metastable state, and also there is a metastable state in the centre of this passage, just can utilize these three metastable states and strong intersection NE BY ENERGY TRANSFER passage to constitute the fluorescence intensity reverse speed characterisstic, and then realize the fluorescence intensity counter-rotating fluorescence falsification preventing of dual wavelength.
The dynamic range of fluorescence intensity counter-rotating
Yb
3+The dynamic range of the fluorescence intensity counter-rotating of X type rare earth nano material is measured in order to following method:
(1) selects for use exciting light EX1 to excite the X ion, make it send stronger short wavelength's fluorescence and more weak long wavelength's fluorescence;
(2) the fluorescence intensity ratio α of detection short wavelength's fluorescence and long wavelength's fluorescence;
(3) select for use exciting light EX2 to excite the X ion, make it send stronger long wavelength's fluorescence and more weak short wavelength's fluorescence;
(4) detect long wavelength's fluorescence and compare γ with the fluorescence intensity counter-rotating of short wavelength's fluorescence;
(5) calculate dynamic range Σ=γ * α that fluorescence intensity is reversed.
Obviously, for the even rare earth material of single kind, because the luminous stability of rare earth material reduces even false proof object causes concentration to reduce luminous intensity because of wearing and tearing, but the ratio value of luminous intensity can not change, so the dynamic range Σ of fluorescence intensity counter-rotating can not change yet.With Yb
3+Er
3+The type rare earth nano material is an example,
4G
11/2Energy level be excited under the situation red green fluorescence intensity counter-rotating than γ=[
4F
9/2/
4S
3/2] (
4G
11/2) and
2H
11/2Energy level be excited normal green red fluorescence intensity ratio α under the situation=[
4S
3/2/
4F
9/2] (
2H
11/2) can not change because of wearing and tearing, the dynamic range Σ=γ * α of red green fluorescence intensity counter-rotating can not change yet.So fluorescence intensity counter-rotative type fluorescence falsification preventing method of the present invention is anti abrasive.
In addition, fluorescence intensity counter-rotative type fluorescence falsification preventing method of the present invention still is anti-defiling.Equally with Yb
3+Er
3+The type rare earth nano material is an example, supposes that false proof body surface coverd with one deck pollution, and its transmittance function is f (x), promptly
4G
11/2Energy level and
2H
11/2The transmitance of the excitation wave strong point of energy level be f (
4G
11/2) and f (
2H
11/2),
4F
9/2Energy level and
4S
3/2The transmitance at the emission wavelength place of energy level be f (
4F
9/2) and f (
4S
3/2), the counter-rotating of fluorescence intensity after then defiling than γ=[f (
4F
9/2) * f (
4G
11/2)/f (
4S
3/2) * f (
4G
11/2)] * [
4F
9/2/
4S
3/2] (
4G
11/2)=[f (
4F
9/2)/f (
4S
3/2)] * [
4F
9/2/
4S
3/2] (
4G
11/2), the fluorescence intensity after defiling normally than α=[f (
4S
3/2) * f (
2H
11/2)/f (
4F
9/2) * f (
2H
11/2)] * [
4S
3/2/
4F
9/2] (
2H
11/2)=[f (
4S
3/2)/f (
4F
9/2)] * [
4S
3/2/
4F
9/2] (
2H
11/2), the dynamic range Σ after defiling=γ * α=[f (
4F
9/2)/f (
4S
3/2)] * [
4F
9/2/
4S
3/2] (
4G
11/2) * [f (
4S
3/2)/f (
4F
9/2)] * [
4S
3/2/
4F
9/2] (
2H
11/2)=[
4F
9/2/
4S
3/2] (
4G
11/2) * [
4S
3/2/
4F
9/2] (
2H
11/2); This has illustrated that the dynamic range Σ after defiling can not change, and promptly dynamic range Σ is anti-defiling.
Fluorescence intensity counter-rotative type fluorescence falsification preventing method
Mix system at representative rare earth is two below, provide the example of concrete enforcement " fluorescence intensity counter-rotative type fluorescence falsification preventing method ".
(a) Yb
3+Er
3+Two systems of mixing
As shown in Figure 5.Select for use exciting light EX1 Er
3+Ion excitation arrives
2H
11/2(or
4F
7/2Deng) energy level, Er
3+Ion relaxes towards through multi-phonon is radiationless
4S
3/2Energy level and send strong green glow EM1 ≈ 550nm, simultaneously
4F
9/2Energy level also has less population and can send more weak ruddiness EM2 ≈ 650nm.
Select for use exciting light EX2 Er again
3+Ion excitation arrives
4G
11/2(or
2G
7/2,
2K
15/2,
4G
9/2Deng) energy level, Er
3+Ion relaxes towards through the intersection NE BY ENERGY TRANSFER
4F
9/2Energy level and send strong ruddiness EM2 ≈ 650nm, simultaneously
4S
3/2Energy level also has less population and can send more weak green glow EM1 ≈ 550nm.
EM3 ≈ 600nm place does not then have fluorescence (background identification).
Detect
2H
11/2(or
4F
7/2Deng) energy level be excited normal green red fluorescence intensity ratio α under the situation=[
4S
3/2/
4F
9/2] (
2H
11/2) and
4G
11/2(or
2G
7/2,
2K
15/2,
4G
9/2Deng) energy level be excited under the situation unusual red green fluorescence intensity counter-rotating than γ=[
4F
9/2/
4S
3/2] (
4G
11/2), and the dynamic range Σ=γ * α of red green fluorescence intensity counter-rotating.
Dynamic range Σ=γ * the α that is tested and appraised red green fluorescence intensity counter-rotating just can differentiate the true and false of measured object, reaches the purpose of fluorescence falsification preventing.
(b) Yb
3+Tb
3+Two systems of mixing
As shown in Figure 6.Select for use exciting light EX1 Tb
3+Ion excitation arrives
5L
9(or
5L
10Deng) energy level, Tb
3+Ion relaxes towards through multi-phonon is radiationless
5D
3Energy level and send strong short wavelength's fluorescence EM1 ≈ 379.4nm, 413.4nm, 436.3nm, 455.7nm, 470.5nm, 480.8nm and 486.0nm.Simultaneously
5D
4Energy level also has less population and can send more weak long wavelength's fluorescence EM2 ≈ 486.2nm, 543.6nm, 583.8nm, 619.2nm, 646.7nm, 666.4nm, 676.4nm.
Select for use exciting light EX2 Tb again
3+Ion excitation arrives
5H
6Deng energy level, Tb
3+Ion relaxes towards through the intersection NE BY ENERGY TRANSFER
5D
4Deng energy level and send strong long wavelength's fluorescence EM2 ≈ 486.2nm, 543.6nm, 583.8nm, 619.2nm, 646.7nm, 666.4nm, 676.4nm.Simultaneously
5D
3Energy level also has less population and can send more weak short wavelength's fluorescence EM1 ≈ 379.4nm, 413.4nm, 436.3nm, 455.7nm, 470.5nm, 480.8nm and 486.0nm.
EM3 ≈ 750nm place does not then have fluorescence (background identification).
Detect
5L
9(or
5L
10Deng) energy level be excited the fluorescence intensity ratio α of normal short wavelength's fluorescence EM1 and long wavelength's fluorescence EM2 under the situation=[
5D
3/
5D
4] (
5L
9) and
5H
6Deng energy level be excited the unusual fluorescence intensity counter-rotating of long wavelength's fluorescence EM2 and short wavelength's fluorescence EM1 under the situation than γ=[
5D
4/
5D
3] (
5H
6), and the dynamic range Σ=γ * α of fluorescence intensity counter-rotating.
Dynamic range Σ=γ * the α that is tested and appraised the fluorescence intensity counter-rotating just can differentiate the true and false of measured object, reaches the purpose of fluorescence falsification preventing.
(c) Yb
3+Eu
3+Two systems of mixing
As shown in Figure 7.Select for use exciting light EX1 Eu
3+Ion excitation arrives
5G
6(or
5L
6Deng) energy level, Eu
3+Ion relaxes towards through multi-phonon is radiationless
5D
3(etc.) energy level and send strong short wavelength's fluorescence EM1 ≈ 410.6nm, 417.0nm, 428.7nm, 444.7nm, 464.4nm, 487.7nm and 514.2nm.Simultaneously
5D
1(etc.) energy level also has less population and can send more weak long wavelength's fluorescence EM2 ≈ 525.6nm, 536.0nm, 555.5nm, 582.7nm, 617.1nm, 658.8nm, 708.2nm.
Long wavelength's fluorescence EM2 selects for use
5D
1The luminous of energy level is to select preferably,
5D
2Energy level and
5D
0Energy level (etc.) luminous also can selecting for use be used as long wavelength's fluorescence EM2, they are respectively:
5D
2The luminous of energy level is 465.5nm, 473.7nm, 488.8nm, 509.8nm, 535.9nm, 567.1nm and 603.3nm;
5D
0The luminous of energy level is 578.3nm, 591.0nm, 614.7nm, 648.2nm, 691.1nm, 743.8nm and 807.4nm.
Select for use exciting light EX2 Eu again
3+Ion excitation arrives
5H
6Deng energy level, Eu
3+Ion relaxes towards through the intersection NE BY ENERGY TRANSFER
5D
1Energy level (or
5D
2Deng energy level) and send strong long wavelength's fluorescence EM2 ≈ 525.6nm, 536.0nm, 555.5nm, 582.7nm, 617.1nm, 658.8nm, 708.2nm.Simultaneously
5D
3Energy level also has less population and can send more weak short wavelength's fluorescence EM1 ≈ 410.6nm, 417.0nm, 428.7nm, 444.7nm, 464.4nm, 487.7nm and 514.2nm.
EM3 ≈ 850nm place does not then have fluorescence (background identification).
Detect
5G
6(or
5L
6Deng) energy level be excited the fluorescence intensity ratio α of normal short wavelength's fluorescence EM1 and long wavelength's fluorescence EM2 under the situation=[
5D
3/
5D
1] (
5G
6) and
5H
6Deng energy level be excited the unusual fluorescence intensity counter-rotating of long wavelength's fluorescence EM2 and short wavelength's fluorescence EM1 under the situation than γ=[
5D
1/
5D
3] (
5H
6), and the dynamic range Σ=γ * α of fluorescence intensity counter-rotating.
Dynamic range Σ=γ * the α that is tested and appraised the fluorescence intensity counter-rotating just can differentiate the true and false of measured object, reaches the purpose of fluorescence falsification preventing.
Embodiment
Below with reference to embodiment the present invention is described, but protection scope of the present invention is not limited by the examples.
The preparation of sample:
Adopt Yuhu Wang and Junichi Ohwaki at Appl.Phys.Lett., disclosed method prepares oxyfluoride glass ceramic (FOV) sample among the Vol.63 (1993) 326.At first at high temperature prepare oxyfluoride glass (FOG) sample, oxyfluoride glass is by silicon oxide sio
2And lead fluoride PbF
2, zinc fluoride ZnF
2, fluoridize lutetium LuF
3, fluoridize ytterbium YbF
3, fluoridize erbium ErF
3Constitute.All raw materials are high purity reagent, and raw material is placed in the platinum crucible, 900 ℃ of following fusions 100 minutes, are poured over cooling rapidly in the iron pan then, have so just obtained the oxyfluoride glass sample.And then the oxyfluoride glass sample at nucleation temperature T
gJust obtained oxyfluoride glass ceramic (FOV) sample through thermal treatment in 7 hours near=389 ℃.
In following test, select for use three kinds to be used for rare earth nano phase oxyfluoride glass ceramic: [1] Er (0.5) Yb (3): FOV, [2] Er (0.5) Yb (1): FOV and [3] Er (0.5): FOV, wherein, Er (0.5) Yb (3): the volumetric molar concentration of FOV sample is the Er of 0.5mol%
3+Yb with 3mol%
3+Choose three kinds of rare earth oxyfluoride glass: [4] Er (0.5) Yb (3): FOG, [5] Er (0.5) Yb (1): FOG and [6] Er (0.5): FOG, and two kinds of ZBLAN (Zr-Ba-La-Al-Na base fluoride glass) glass material [7] Er (0.3) Yb (3): ZBLAN and [8] Er (0.3): ZBLAN, sample as a comparison.
The Stokes fluorescence spectral measuring:
The Stokes fluorescence spectrum of sample is to be measured by the fluorescence spectrophotometer with double grating monochromator.The light source of fluorescence spectrophotometer is traditional xenon lamp.The front surface fluorescent measurement is adopted in this test, and the excitation light irradiation of xenon lamp is on the front surface of sample, and the fluorescence that the sample front surface is sent is collected through system light path, and the direction of observation of fluorescence approaches the incident direction of exciting light.Test condition remains unchanged to guarantee that measurement result can compare.
Table 1 has provided all [1] Er (0.5) Yb (3): FOV, [2] Er (0.5) Yb (1): FOV, [3] Er (0.5): FOV, [4] Er (0.5) Yb (3): FOG, [5] Er (0.5) Yb (1): FOG, [6] Er (0.5): FOG, [7] Er (0.3) Yb (3): ZBLAN and [8] Er (0.3): the dynamic range Σ of the fluorescence relative intensity of the Stokes fluorescence emission spectrum of eight kinds of samples of ZBLAN and fluorescence intensity counter-rotating.F[in the table
4S
3/2] (
4G
11/2) representative
4G
11/2Energy level is excited under the situation
4S
3/2The luminous intensity of energy level, F[
4F
9/2] (
4G
11/2) representative
4G
11/2Energy level is excited under the situation
4F
9/2The luminous intensity of energy level, F[
4S
3/2] (
2H
11/2) representative
2H
11/2Energy level is excited under the situation
4S
3/2The luminous intensity of energy level, F[
4F
9/2] (
2H
11/2) representative
2H
11/2Energy level is excited under the situation
4F
9/2The luminous intensity of energy level.γ=F[
4F
9/2/
4S
3/2] (
4G
11/2) be F[
4F
9/2] (
4G
11/2) and F[
4S
3/2] (
4G
11/2) ratio value, α=F[
4S
3/2/
4F
9/2] (
2H
11/2) be F[
4S
3/2] (
2H
11/2) and F[
4F
9/2] (
2H
11/2) ratio value.
Table 1.
| Sample number into spectrum | F( 4S 3/2) 4G11/2Luminous intensity | F( 4F 9/2) 4G11/2Luminous intensity | γ is compared in counter-rotating | F( 4S 3/2) 2H11/2Luminous intensity | F( 4F 9/2) 2H11/2Luminous intensity | Normally than α | Dynamic range Σ=γ * α |
| [1] | 7.00×10 6 | 8.37×10 7 | 1.20×10 1 | 8.80×10 6 | 2.45×10 5 | 3.60×10 1 | 4.32×10 2 |
| [2] | 3.04×10 7 | 1.49×10 6 | 4.92×10 -2 | 1.28×10 7 | 4.08×10 5 | 3.15×10 1 | 1.55 |
| [3] | 2.97×10 7 | 3.93×10 5 | 1.32×10 -2 | 8.48×10 6 | 2.76×10 5 | 3.07×10 1 | 4.05×10 -1 |
| [4] | 1.58×10 7 | 2.73×10 6 | 1.73×10 -1 | 6.26×10 6 | 2.36×10 5 | 2.22×10 1 | 4.60 |
| [5] | 2.69×10 7 | 7.82×10 5 | 2.91×10 -2 | 1.11×10 7 | 3.91×10 5 | 2.83×10 1 | 8.23×10 -1 |
| [6] | 3.26×10 7 | 4.42×10 5 | 1.36×10 -2 | 1.37×10 7 | 2.69×10 5 | 5.09×10 1 | 6.92×10 -1 |
| [7] | 1.35×10 8 | 4.27×10 6 | 3.17×10 -2 | 7.61×10 7 | 2.44×10 6 | 3.12×10 1 | 9.89×10 -1 |
| [8] | 1.54×10 8 | 2.15×10 6 | 1.40×10 -2 | 7.83×10 7 | 1.32×10 6 | 5.92×10 1 | 8.27×10 -1 |
Remarks: the counter-rotating than γ=[F (
4F
9/2)/F (
4S
3/2)] (
4G
11/2); Normally than α=[F (
4S
3/2)/F (
4F
9/2)] (
4F
7/2); Dynamic range Σ=γ * α.
From table 1 obviously as seen, [2] Er (0.5) Yb (1): FOV, [3] Er (0.5): FOV, [4] Er (0.5) Yb (3): FOG, [5] Er (0.5) Yb (1): FOG; [6] Er (0.5): FOG, [7] Er (0.3) Yb (3): ZBLAN and seven kinds of specimen materials of [8] Er (0.3): ZBLAN all do not have to occur significantly " fluorescence intensity counter-rotating " phenomenon, [1] Er (0.5) Yb (3) only: " red green fluorescence intensity counter-rotating " characteristic appears significantly in FOV nanophase oxyfluoride glass ceramic, [1] Er (0.5) Yb (3): the dynamic range Σ of " the red green fluorescence intensity counter-rotating " of FOV nanophase oxyfluoride glass ceramic is bigger about 100 to 1000 times than other material.
What wherein especially merit attention has 2 points: the first, for [4] Er (0.5) Yb (3): FOG oxyfluoride glass sample, though Er
3+Ion Yb
3+The concentration of ion and parent matrix fully with [1] Er (0.5) Yb (3): FOV is the same, but the dynamic range Σ of its fluorescence intensity counter-rotating is than [1] Er (0.5) Yb (3): FOV is little 100 times, illustrate that micritization forms the generation that the nanophase glass ceramics reverses to fluorescence intensity and played critical effect; And, then do not have the fluorescence intensity reversal development fully for [7] Er (0.3) Yb (3): ZBLAN.The second, and [1] Er (0.5) Yb (3): FOV compares, [2] Er (0.5) Yb (1): the FOV sample only is Yb
3+The density loss of ion 3 times, but the dynamic range Σ of its fluorescence intensity counter-rotating is than [1] Er (0.5) Yb (3): FOV is little 279 times, illustrate that it is the strong Yb that depends on that fluorescence intensity is reversed
3+The concentration of ion, it is individual very strong nonlinear luminescence kinetics process.
Wear-resistant anti-defiling and fail-test:
Select representational [1] Er (0.5) Yb (3): FOV, [2] Er (0.5) Yb (1): FOV and three kinds of samples of [7] Er (0.3) Yb (3): ZBLAN carry out wear-resistant anti-defiling and fail-test.In test, color filter is placed on before the front surface of sample, measures the spectral signal of sample by system.
The influence of selecting for use QB21 to wear and tear and defile as simulation is with the wear-resistant anti-characteristic of defiling of check fluorescence intensity counter-rotative type fluorescence falsification preventing method.The QB21 color filter is a kind of band-pass filter, to 378.9nm, and 486.7nm, the transmitance of 540.5nm and 667.9nm wavelength light is respectively 80%, 90%, 70% and 3% successively approximately.
Selecting the ZJB320 color filter for use mainly is influence for the detection system light path, with the reliability of check fluorescence intensity counter-rotative type fluorescence falsification preventing method.The ZJB320 color filter is to 378.9nm, 486.7nm, and the transmitance of 540.5nm and 667.9nm wavelength light all is 90% approximately.
Be provided with three kinds of trystates respectively, promptly do not put the pure sample product state of color filter, the wear-resistant anti-trystate and add the system reliability proofing state of ZJB320 color filter of defiling that adds the QB21 color filter.Therefore have nine groups of tests, be respectively: [1] Er (0.5) Yb (3): FOV; [1b] Er (0.5) Yb (3): FOV+QB21; [1c] Er (0.5) Yb (3): FOV+ZJB320; [2] Er (0.5) Yb (1): FOV; [2b] Er (0.5) Yb (1): FOV+QB21; [2c] Er (0.5) Yb (1): FOV+ZJB320; [7] Er (0.3) Yb (3): ZBLAN; [7b] Er (0.3) Yb (3): ZBLAN+QB21; [7c] Er (0.3) Yb (3): ZBLAN+ZJB320.In these nine groups tests, measure three kinds of samples respectively at the 486.7nm excited by visible light
4F
7/2Energy level and at the 378.9nm ultraviolet excitation
4G
11/2Under the energy level situation,
4S
3/2Energy level 540.5nm green fluorescence and
4F
9/2The intensity of energy level 667.9nm red fluorescence, and calculate normal fluorescence intensity ratio α, fluorescence intensity is reversed than γ, and the dynamic range Σ=γ * α of fluorescence intensity counter-rotating.All test findings are listed in the table 2.
Table 2. relative intensity of fluorescence F, normally than α=[F (
4S
3/2)/F (
4F
9/2)] (
4F
7/2), the counter-rotating than γ=[F (
4F
9/2)/F (
4S
3/2)] (
4G
11/2) and dynamic range Σ=γ * α.
| Test number | F[ 4S 3/2]( 4G 11/2) luminous intensity | F[ 4F 9/2]( 4G 11/2) luminous intensity | Counter-rotating ratio: γ | F[ 4S 3/2]( 4F 7/2) luminous intensity | F[ 4F 9/2]( 4F 7/2) luminous intensity | Normally than α | Dynamic range Σ=γ * α | ΔΣ(％) |
| [1] | 1.246×10 7 | 1.444×10 8 | 1.159×10 1 | 1.848×10 7 | 3.211×10 5 | 4.964×10 1 | 5.753×10 2 | - |
| [1b] | 9.814×10 6 | 6.430×10 6 | 6.552×10 -1 | 1.677×10 7 | 1.850×10 4 | 9.064×10 2 | 5.938×10 2 | +3.2 |
| [1c] | 1.562×10 7 | 1.897×10 8 | 1.215×10 1 | 2.156×10 7 | 4.416×10 5 | 4.882×10 1 | 5.931×10 2 | +3.1 |
| [2] | 5.541×10 7 | 2.781×10 6 | 5.019×10 -2 | 1.537×10 7 | 4.624×10 5 | 3.325×10 1 | 1.669 | - |
| [2b] | 6.246×10 7 | 1.699×10 5 | 2.720×10 -3 | 2.019×10 7 | 3.295×10 4 | 6.127×10 2 | 1.667 | -0.1 |
| [2c] | 9.320×10 7 | 4.864×10 6 | 5.219×10 -2 | 2.445×10 7 | 7.500×10 5 | 3.260×10 1 | 1.701 | +1.9 |
| [7] | 4.052×10 8 | 1.243×10 7 | 3.067×10 -2 | 9.134×10 7 | 2.754×10 6 | 3.317×10 1 | 1.017 | - |
| [7b] | 5.867×10 8 | 9.696×10 5 | 1.653×10 -3 | 1.449×10 8 | 2.381×10 5 | 6.083×10 2 | 1.005 | -0.1 |
| [7c] | 8.535×10 8 | 2.893×10 7 | 3.390×10 -2 | 1.770×10 8 | 5.507×10 6 | 3.214×10 1 | 1.090 | 7.2 |
From above-mentioned test findings as can be seen, no color filter or add color filter before sample, though great changes will take place for fluorescence intensity, also great changes will take place for α and γ, dynamic range Σ but is constant substantially.For [1] Er (0.5) Yb (3): FOV, place QB21 and ZJB320 color filter, the changes delta Σ of dynamic range Σ has only+and 3.2% and+3.1%.For Er (0.5) Yb (1): FOV, place QB21 and ZJB320 color filter, the changes delta Σ of dynamic range Σ has only-0.1% and+1.9%, for [7] Er (0.3) Yb (3): ZBLAN, add QB21 and ZJB320 color filter, the changes delta Σ of dynamic range Σ has only-0.1% and 7.2%.This has just confirmed that fluorescence intensity counter-rotative type fluorescence falsification preventing method has the wear-resistant anti-characteristic of defiling, and has confirmed that also fluorescence intensity counter-rotative abrasion-proof bedaub-resistant fluorescence anti-counterfeiting method of the present invention is feasible simultaneously.
In addition, because the present invention has adopted unique fluorescence intensity inversion technique as method for anti-counterfeit, this technology is not to adopt common material or simple rare earth ion combination to forge, make that fakement is difficult to make, therefore, the reliability of fluorescence intensity counter-rotating fluorescence falsification preventing method of the present invention is fine, has a good application prospect.
Claims (8)
1. wear-resistant anti-fluorescence falsification preventing method of defiling of dual wavelength excited fluorescent intensity counter-rotative type, this method adopts Yb
3+X type rare earth nano material is as the fluorescence falsification preventing material, and wherein X is for removing Yb
3+Another kind of rare earth element ion in addition, the dynamic range of utilizing the fluorescence intensity counter-rotating of this rare earth nano material and fluorescence intensity counter-rotating wear and tear or defile after constant substantially characteristic carry out fluorescence falsification preventing, described method comprises:
(1) selects for use exciting light EX1 to excite the X ion, make it send stronger short wavelength's fluorescence EM1 and more weak long wavelength's fluorescence EM2;
(2) short wavelength's fluorescence EM1 under detection exciting light EX1 excites and the fluorescence intensity ratio α of long wavelength's fluorescence EM2;
(3) select for use exciting light EX2 to excite the X ion, make it send stronger long wavelength's fluorescence EM2 and more weak short wavelength's fluorescence EM1;
(4) the long wavelength's fluorescence EM2 under detection exciting light EX2 excites compares γ with the fluorescence intensity counter-rotating of short wavelength's fluorescence EM1; With
(5) calculate dynamic range ∑=γ * α that fluorescence intensity is reversed.
Wherein the dynamic range ∑ of fluorescence intensity counter-rotating in wearing and tearing or the variation range delta ∑ before and after defiling in 32%.
2. according to the fluorescence falsification preventing method of claim 1, wherein said Δ ∑ is in 19%.
3. according to the fluorescence falsification preventing method of claim 1, wherein said Δ ∑ is in 10%.
4. according to the fluorescence falsification preventing method of claim 1, wherein said X comprises Er
3+, Eu
3+And Tb
3+
5. according to the fluorescence falsification preventing method of claim 1, wherein said X is Er
3+, and described method comprises:
(1) select for use exciting light EX1 Er
3+Ion excitation arrives
2H
11/2Energy level, Er
3+Ion relaxes towards through multi-phonon is radiationless
4S
3/2Energy level and send stronger short wavelength's fluorescence EM1 ≈ 550nm, simultaneously
4F
9/2Energy level also has less population and can send more weak long wavelength's fluorescence EM2 ≈ 650nm;
(2) detect
2H
11/2Energy level be excited the fluorescence intensity ratio α of normal short wavelength's fluorescence EM1 and long wavelength's fluorescence EM2 under the situation=[
4S
3/2/
4F
9/2] (
2H
11/2);
(3) select for use exciting light EX2 Er
3+Ion excitation arrives
4G
11/2Energy level, Er
3+Ion relaxes towards through the intersection NE BY ENERGY TRANSFER
4F
9/2Energy level and send stronger long wavelength's fluorescence EM2 ≈ 650nm, simultaneously
4S
3/2Energy level also has less population and can send more weak short wavelength's fluorescence EM1 ≈ 550nm;
(4) detect
4G
11/2Energy level be excited the fluorescence intensity counter-rotating of long wavelength's fluorescence EM2 and short wavelength's fluorescence EM1 under the situation than γ=[
4F
9/2/
4S
3/2] (
4G
11/2); With
(5) calculate dynamic range ∑=γ * α that fluorescence intensity is reversed.
6. according to the fluorescence falsification preventing method of claim 1, wherein said X is Tb
3+, and described method comprises:
(1) select for use exciting light EX1 Tb
3+Ion excitation arrives
5L
9Energy level, Tb
3+Ion relaxes towards through multi-phonon is radiationless
5D
3Energy level and send stronger short wavelength's fluorescence EM1 ≈ 379.4nm, 413.4nm, 436.3nm, 455.7nm, 470.5nm, 480.8nm and 486.0nm, simultaneously
5D
4Energy level also has less population and can send more weak long wavelength's fluorescence EM2 ≈ 486.2nm, 543.6nm, 583.8nm, 619.2nm, 646.7nm, 666.4nm, 676.4nm;
(2) detect
5L
9Energy level be excited the fluorescence intensity ratio α of normal short wavelength's fluorescence and long wavelength's fluorescence under the situation=[
5D
3/
5D
4] (
5L
9);
(3) select for use exciting light EX2 Tb
3+Ion excitation arrives
5H
6Energy level, Tb
3+Ion relaxes towards through the intersection NE BY ENERGY TRANSFER
5D
4Energy level and send stronger long wavelength's fluorescence EM2 ≈ 486.2nm, 543.6nm, 583.8nm, 619.2nm, 646.7nm, 666.4nm, 676.4nm, simultaneously
5D
3Energy level also has less population and can send more weak short wavelength's fluorescence EM1 ≈ 379.4nm, 413.4nm, 436.3nm, 455.7nm, 470.5nm, 480.8nm and 486.0nm;
(4) detect
5H
6Energy level be excited the fluorescence intensity counter-rotating of long wavelength's fluorescence and short wavelength's fluorescence under the situation than γ=[
5D
4/
5D
3] (
5H
6); With
(5) calculate dynamic range ∑=γ * α that fluorescence intensity is reversed.
7. according to the fluorescence falsification preventing method of claim 1, wherein said X is Eu
3+, and described method comprises:
(1) select for use exciting light EX1 Eu
3+Ion excitation arrives
5G
6Energy level, Eu
3+Ion relaxes towards through multi-phonon is radiationless
5D
3Energy level and send stronger short wavelength's fluorescence EM1 ≈ 410.6nm, 417.0nm, 428.7nm, 444.7nm, 464.4nm, 487.7nm and 514.2nm, simultaneously
5D
1Energy level also has less population and can send more weak long wavelength's fluorescence EM2 ≈ 525.6nm, 536.0nm, 555.5nm, 582.7nm, 617.1nm, 658.8nm, 708.2nm;
(2) detect
5G
6Energy level be excited the fluorescence intensity ratio α of normal short wavelength's fluorescence and long wavelength's fluorescence under the situation=[
5D
3/
5D
1] (
5G
6);
(3) select for use exciting light EX2 Eu
3+Ion excitation arrives
5H
6Energy level, Eu
3+Ion relaxes towards through the intersection NE BY ENERGY TRANSFER
5D
1Energy level and send stronger long wavelength's fluorescence EM2 ≈ 525.6nm, 536.0nm, 555.5nm, 582.7nm, 617.1nm, 658.8nm, 708.2nm; Simultaneously
5D
3Energy level also has less population and can send more weak short wavelength's fluorescence EM1 ≈ 410.6nm, 417.0nm, 428.7nm, 444.7nm, 464.4nm, 487.7nm and 514.2nm;
(4) detect
5H
6Energy level be excited the fluorescence intensity counter-rotating of long wavelength's fluorescence and short wavelength's fluorescence under the situation than γ=[
5D
1/
5D
3] (
5H
6); With
(5) calculate dynamic range ∑=γ * α that fluorescence intensity is reversed.
8. according to the fluorescence falsification preventing method of claim 1, wherein said Yb
3+X type rare earth nano material is Yb
3+The two nanophase oxyfluoride glass ceramics of mixing of X type rare earth.
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| 陈晓波等.ErYb:氟氧化物玻璃陶瓷中上转换发光特征饱和现象的综合分析.光谱学与光谱分析25 2.2005,25(2),161-165. |
| 陈晓波等.ErYb:氟氧化物玻璃陶瓷中上转换发光特征饱和现象的综合分析.光谱学与光谱分析25 2.2005,25(2),161-165. * |
| 陈晓波等.氟氧化物玻璃陶瓷中交叉能量传递与荧光防伪的初步研究.物理学报49 12.2000,49(12),2488-2492. |
| 陈晓波等.氟氧化物玻璃陶瓷中交叉能量传递与荧光防伪的初步研究.物理学报49 12.2000,49(12),2488-2492. * |
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