CN103649729B - Method and apparatus by light emitting phosphor compound checking article - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 50
- -1 phosphor compound Chemical class 0.000 title claims description 141
- 230000005855 radiation Effects 0.000 claims abstract description 158
- 238000001228 spectrum Methods 0.000 claims abstract description 153
- 150000002500 ions Chemical class 0.000 claims abstract description 140
- 230000005284 excitation Effects 0.000 claims abstract description 66
- 238000012545 processing Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims description 70
- 230000003287 optical effect Effects 0.000 claims description 17
- 229910052691 Erbium Inorganic materials 0.000 claims description 11
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 10
- 239000002223 garnet Substances 0.000 claims description 10
- 229910052689 Holmium Inorganic materials 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 7
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
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- 150000004645 aluminates Chemical class 0.000 claims description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 4
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- 238000007689 inspection Methods 0.000 claims description 3
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- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
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- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
For the method and apparatus of item authentication, it includes excitation radiation generator, and the certain area of these article is exposed to excitation radiation by it；With at least two radiation detector, its detection from described region be in the first bands of a spectrum and the transmitting radiation that is in the second not overlapping with these first bands of a spectrum bands of a spectrum.These first bands of a spectrum are corresponding to the first sub-bands of a spectrum of transmitting of emitting ions, and these second bands of a spectrum are corresponding to the second sub-bands of a spectrum of transmitting of identical emitting ions.Processing system calculates fiducial value, this value represents the relationship (such as ratio) between the first intensity launching radiation and the second intensity launching radiation being in the second bands of a spectrum being in the first bands of a spectrum, and determines whether this fiducial value is consistent with certificate parameter.When this fiducial value meets certificate parameter, these article are accredited as being believable.
Description
Cross-Reference to Related Applications
This application claims U.S.'s non-provisional application sequence number 13/537414 filed in 29 days June in 2012 and July 15 in 2011
The rights and interests of U.S. Provisional Application sequence number 61/508302 filed in.
Technical field
The present invention relates generally to radiation-emitting compound and the method and apparatus of the checking for them.
Background technology
Light emitting phosphor compound is such compound, and by encouraging this compound by extra power, it can be launched
Being in of detectable amount be infrared, visible and/or radiation in ultraviolet spectra.Typical light emitting phosphor compound at least includes main
Lattice (host crystal lattice), emitting ions (emitting ion) (ion of such as rare earth metal) and at some
Situation include " sensitization (sensitizing) " ion (ion of such as transition metal or the ion of different rare earth metals,
It can absorb and transfer energy into rare earth metal emitting ions).Producing radiation by phosphor compound is by as follows
Complete: by one or more emitting ions or by host lattice and the one or both in one or more sensitized ions
Absorb incident radiation, energy is transferred to emitting ions from host lattice/sensitized ions, and radiated by emitting ions and shifted
Energy.
The selected component of phosphor compound causes this compound to have specific performance, including the certain wave of its excitation energy
One or more peaks in long (" excitation radiation "), and the energy launched by the emitting ions of this phosphor compound specific
Spectral position (" launching radiation ").The most each ion can have transmitting in whole host lattices.There is many examples, its
In have and launch the radiation of probability and be quenched, or be such from absorbing ion or host lattice and transfer to the energy of emitting ions
Difference, to such an extent as to be little to observe radiation effect.In other host lattice, radiation effect can be very big, and quantum effect
Rate is close to unanimously.
For specific phosphor compound (it produces observable transmitting and radiates), in its launch in radiation
Individual or multiple peak one or more spectral positions (i.e. its " spectral signature ") may be used for from different compounds unique
Identify this phosphor compound.This spectral signature is mainly due to rare earth ion (or multiple rare earth ion).But due to
Host lattice, for the impact of various ions, produces impact, Ke Nengcun typically via crystal field strength and division (splitting)
At light perturbation of spectrum.Also it is such for launching the temporary transient behavior of radiation.
The spectral characteristic of some phosphor compound uniquenesses is make them highly suitable for checking or qualification has specific
It is worth or the article (such as banknote, passport, biological sample etc.) of importance.Therefore there is the luminescent phosphor of known spectra feature
Body compound has been incorporated in various types of article, strengthens Counterfeit Item or the fakement detecting this kind of article, or
Follow the trail of and identify the ability of these article.Such as light emitting phosphor compound with additive, coating and printing or with other
The form of the checking feature that mode applies is attached in various types of article.
Article including light emitting phosphor compound can use custom-designed checking device to verify.More particularly,
Known phosphor compound (such as " checking is used " phosphor compound) can be attached to its " authentic " article by manufacturer
In.The checking device being configured to detect the credibility of this kind of article has can absorb relevant to checking phosphor compound
Property the wavelength of excitation radiation and launch the knowledge (information such as stored) of spectral characteristic of radiation.When being provided with for checking
During sample article, these article are exposed to excitation radiation by this checking device, and this radiation has such wavelength, and it is corresponding to directly
Or indirectly guide the known wavelength of the desired light emitting phosphor Absorption Characteristics launching radiation.This checking device perception and sign are used
Spectrum parameter in any transmitting radiation that can be produced by these article.When the spectral signature launching radiation detected is in inspection
When the certificate parameter scope of measurement equipment (its corresponding to checking with phosphor compound (referred to as " detection parameter space ")) is interior, this thing
Product can be considered believable (authentic).On the contrary, when this checking device fail perception expection be in detection parameter space in letter
Number time, these article can be considered incredible (unauthentic) article of personation (that such as forge or).
Above-mentioned technology is very effective when detection is with the relative offending counterfeit of prevention and personation activity.But,
The individual with suitable resource and device may can use spectral technique to determine the component of some phosphor compound.So
After, this phosphor compound can be replicated and be applied to incredible article, therefore having injured otherwise by specific phosphorus
The benefit of the checking that body of light compound provides.Therefore, although the phosphor compound having been developed for many helps with above-mentioned
Mode checking article, but it is desirable to be developed for other compound and the technology of checking article, it can make to copy and personation
Behavior is more difficult from, and/or it can be proved to be of value to the article identified and follow the trail of special concern.Additionally, the present invention
Other desirable features and characteristics is based on detailed description of the invention subsequently and claims, in conjunction with accompanying drawing and the present invention
This background will become clear from.
Summary of the invention
A kind of embodiment for the method for checking article comprises the steps: that the certain area making these article is exposed to
Excitation radiation, and detection being in the first bands of a spectrum and being in not overlapping with these first bands of a spectrum second from region described in these article
Transmitting radiation (emitted radiation) of bands of a spectrum, wherein these first bands of a spectrum are corresponding to the first transmitting son spectrum of emitting ions
Band, and these second bands of a spectrum are corresponding to the second sub-bands of a spectrum of transmitting of this emitting ions.The method farther includes to calculate fiducial value, should
Value represents the first intensity launching radiation being in the first bands of a spectrum and the last the second launching radiation being in the second bands of a spectrum
Relationship between degree, and determine whether this fiducial value is consistent with certificate parameter.When this fiducial value meets certificate parameter
Time, these article are accredited as believable.
In another embodiment, the first intensity is the first integral intensity in the first bands of a spectrum, and the second intensity is second
Second integral intensity in bands of a spectrum.In yet another embodiment, the first intensity is predetermined instant after stopping providing excitation radiation
Measure the first absolute intensity, and the second intensity be predetermined instant measure the second absolute intensity.
In yet another embodiment, the first bands of a spectrum and the second bands of a spectrum are corresponding to the single ionic selected from elements below
The emission band of (single ion): chromium, manganese, cobalt, nickel, cerium, praseodymium, neodymium, samarium, europium, terbium, dysprosium, holmium, erbium, thulium and ytterbium.In another reality
Executing in scheme, the first bands of a spectrum and the second bands of a spectrum are corresponding to single ionic after being substituted in following host lattice material
Emission band: oxide, fluoride, oxysulfide, halogenide, borate, silicate, gallate, phosphate, vanadic acid
Salt, oxyhalide, aluminate, molybdate, tungstates, garnet and niobates.In still another embodiment, the first bands of a spectrum and
Two bands of a spectrum are corresponding to the emission band of single ionic after being substituted in following host lattice material: oxygen yttrium sulfide, yttrium
Aluminium garnet and Gd-Ga garnet.
In yet another embodiment, the step of calculating fiducial value includes the ratio calculating between the first intensity and the second intensity
Rate, wherein said fiducial value is this ratio.
A kind of embodiment for the equipment of checking article comprises excitation radiation generator, the first transmitting radiation detection
Device, the second transmitting radiation detector and processing system.This excitation radiation generator is configured to excitation radiation is guided article
Certain area.This first is launched radiation detector and is configured to detect being in the first bands of a spectrum of described region from these article
Transmitting radiation, wherein these first bands of a spectrum corresponding to emitting ions first transmitting sub-bands of a spectrum.Second launches radiation detector joins
Put the transmitting being in the second not overlapping with the first bands of a spectrum bands of a spectrum radiation for detecting the described region from these article, its
In these second bands of a spectrum corresponding to emitting ions second transmitting sub-bands of a spectrum.This processing system is configured to calculate fiducial value, this value
Represent the first intensity launching radiation being in the first bands of a spectrum and the second intensity launching radiation being in the second bands of a spectrum
Between relationship, to determine whether this fiducial value is consistent with certificate parameter, and meet certificate parameter when this fiducial value
Time, article are accredited as believable.
In another embodiment, this processing system is configured to the ratio by calculating between the first intensity and the second intensity
Rate calculates fiducial value, and wherein this fiducial value is described ratio.
In yet another embodiment, this equipment also includes optical element, and it is configured to be separated into described transmitting radiation
First light beam and the second light beam, this first light beam includes the light being in the first bands of a spectrum, and this second light beam includes being in second
Light in bands of a spectrum, wherein the first light beam is directed to the first radiation detector, and the second light beam is directed to the second radiation detector.
Accompanying drawing explanation
Embodiment of the present invention describe hereinafter in conjunction with following accompanying drawing, and the most same numeral illustrates same
The element of sample, and wherein:
Fig. 1 shows the possible component of the phosphor compound according to various exemplary；
Fig. 2 is to illustrate according to a kind of embodiment at the figure of the emissive porwer of first wave strong point, and it is along with various exemplary
The doping percentage ratio of phosphor compound and change；
Fig. 3 is to illustrate the figure according to a kind of embodiment emissive porwer at second wave length, and it is exemplary along with Fig. 2's
The doping percentage ratio of phosphor compound and change；
Fig. 4 is the ratio between illustrating according to a kind of embodiment emissive porwer at first wave length and second wave length
Figure, it changes along with the doping percentage ratio of the exemplary phosphor compound of Fig. 2；
Fig. 5 is the figure illustrating the emissive porwer according to a kind of embodiment, and it is along with the exemplary phosphor being in Fig. 2
Wavelength in first bands of a spectrum of compound and change；
Fig. 6 is the figure illustrating the emissive porwer according to a kind of embodiment, and it is along with the exemplary phosphor being in Fig. 2
Wavelength in second bands of a spectrum of compound and change；
Fig. 7 is the flow chart of a kind of method for producing phosphor compound according to exemplary；
Fig. 8 is the system for checking article according to a kind of exemplary；
Fig. 9 is the flow chart of a kind of method for carrying out item authentication according to exemplary, and these article can
Comprise phosphor compound；With
Figure 10 shows the sectional view of the article according to a kind of exemplary, its have comprise phosphor, embedding
Checking feature that is that enter and that print.
Detailed description of the invention
The various embodiment of the present invention described further below is merely exemplary in nature, is not intended to limit this
Bright theme or the application of present subject matter and purposes.Additionally, be not intended to be limited in foregoing background part or following
Detailed description in propose any theory.
This document describes light emitting phosphor compound, the article being combined with this compounds and their manufacture and checking
Method.Following phosphor compound may be used for multiple application, includes but not limited to be attached to this kind of phosphor compound
Article strengthen item authentication work (efforts).The embodiment of following phosphor compound each self-contained at least one
The sensitized ions that emitting ions and optional one or more are substituted in host lattice.When one of these phosphor compound expose to the open air
When excitation radiation, this excitation radiation can directly be launched ionic absorption, and/or optionally by one or more sensitized ions
And/or absorbed by host lattice, transfer energy into emitting ions subsequently.No matter excitation radiation is absorbed in which way, this phosphorus
The emitting ions of body of light compound all creates has unique property (such as unique spectral signature and detectable decay
(decay) time constant) transmitting radiation.
After subjected to excitation radiation, many phosphor compound launch be in electromagnetic spectrum visible ray and/or
The detectable radiation of the multiple wavelength in ultraviolet portion.The concentration being in the sub-bands of a spectrum of this electromagnetic spectrum is launched
(concentrated emission) sometimes referred to as " transmitting line ", wherein " sub-bands of a spectrum " are defined herein as expression and are in
Continuous print wave-length coverage in the emission spectrum of described phosphor compound, there occurs that in this wave-length coverage concentration is launched.Example
As erbium ion launches radiation in center is in many sub-bands of a spectrum of multiple wavelength, it is included in 980 nanometers (nm) and 1550nm
Relatively strong transmitting.According to various embodiments, for checking article (it can include this kind of phosphor compound) method and
Equipment includes making the certain area of article be exposed to excitation radiation and detect the transmitting radiation in the described region from these article.More
Especially, after the described region making these article is exposed to excitation radiation, collection is from sending out that the described field emission of these article goes out
Penetrate radiation, and be directed to one or more active regions of one or more photodetector (also referred to herein as " detector ")
On.At each detector, (impinging) of irradiation launches radiation may cross over whole spectral bands or may be across
The most one or more sub-bands of a spectrum (the most through one or more light filters).Each detector produces e-mail
Number, its to be irradiated on detector active region collected by the intensity of radiation be directly proportional.This intensity is herein referred to as
" integrated intensity ".According to a kind of embodiment, checking device purpose is that the integration in the multiple not overlapping spectral bands of detection is strong
Degree, wherein said bands of a spectrum are corresponding to the known emission band of the emitting ions in phosphor compound.Then fiducial value is calculated, its
Represent the relationship between the integrated intensity launching radiation being in multiple bands of a spectrum.In one embodiment, should
Relationship has quantified the relative intensity of the integrated emission radiation in multiple bands of a spectrum of the predetermined instant after stopping excitation.When
When this fiducial value is consistent with certificate parameter, these article are accredited as being believable.Otherwise, these article are accredited as being insincere
's.
As will be described in more detail, a kind of specific embodiment includes detecting and is in two not overlapping bands of a spectrum
Transmitting radiation, wherein fiducial value is to calculate based on two integrated intensity measurement results corresponding to the two bands of a spectrum.?
In other embodiment, launching radiation can detect in the bands of a spectrum that more than two does not overlaps, and fiducial value can be based on
More than two integrated intensity measurement result calculates.It addition, in the specific embodiment of one, this fiducial value represents correspondence
First integral intensity in the first bands of a spectrum and the mathematics ratio of the second integral intensity corresponding to the second bands of a spectrum.Other embodiment party
In case, this fiducial value can be based on the relationship of non-ratio.Finally, although following describes a kind of embodiment, its
Middle use verification method and equipment detect the phosphor compound of the oxygen yttrium sulfide including Er ions, but this Exemplary phosphorescent
Body compound is not intended to be only limited to the application of various embodiments this compound, and for numerous host lattices and transmitting
Ion, various embodiments may be used for detection and launch radiation and carry out item authentication.
As it has been described above, and according to a kind of embodiment, the relative integral launching radiation in multiple bands of a spectrum can be analyzed
Intensity (such as analyzes the ratio launching the integrated intensity radiated in multiple bands of a spectrum), as the basis for checking article.Make
May be more desirable than the absolute integral strength assessment in single bands of a spectrum with the analysis of relative integral intensity, because various factors
(it it is not easily possible to take (accountable for) into account) may affect the precision of absolute integral intensity readouts.Lift several
For the example of individual factor, the intensity such as launching radiation may be by the dirt on article or checking feature and/or mill
Damage, the change in the printing of checking feature, optics geometry, the reflectance of base material, the light scattering in base material, item sizes and shape
The relativeness of the penetration depth of shape, base material thickness and excitation radiation, and the impact of the power level of laser instrument.Therefore in one
In embodiment, selecting the relationship being used for calculating fiducial value is such relationship, and it is largely independent
Integrated intensity value in any single bands of a spectrum.Such as ratio between the integrated intensity value in relationship is multiple bands of a spectrum
During rate, this rate value is more sane (robust) more than the absolute value of any one integrated value as the instruction of credibility.
Following phosphor compound and the embodiment for the method and apparatus of their detection improve and can be used for
The multiformity of the available material of checking.In addition to damping time constant, multiple bands of a spectrum (which characterizes phosphorescence discussed herein
Body chemical embodiments) in emissive porwer between relationship may serve as verify the detectable amount of purpose.
Fig. 1 shows the possible component of the phosphor compound 100 according to various exemplary.According to various
Embodiment, phosphor compound 100 includes host lattice material 130 and emitting ions 110 (emitting ions i.e. substituted).One
Planting in selectable embodiment, phosphor compound 100 can comprise more than a kind of emitting ions 110.Phosphor compound
100 can also include other material (such as one or more sensitized ions) equally, but other material this kind of is not concrete at this
Discuss.
According to a kind of embodiment, the emitting ions 110 in phosphor compound 100 is by can be at multiple different wave lengths
The transmitting that place detects characterizes.The most described wavelength is sufficiently separated, so that the dissimilar or photodetector of kind
Can be used for measuring the emitting performance of phosphor compound 100, but it is expected to such embodiment, can use wherein
The transmitting in different spectral bands measured by the photodetector of same type or kind.According to a kind of embodiment, phosphor chemical combination
Thing 100 includes single host lattice material 130 and single rare earth emitting ions 110, and it is spectrally from obtaining relatively far away from
Multiple bands of a spectrum of (such as at a distance of at least 300nm) produce and launches, and.It addition, in one embodiment, by having point
Prop up and characterize emitting ions than the transmitting of (branching ratio) (i.e. ratio between emissive porwer in different spectral bands)
110, it is the majorant (strong function) of adulterant percentage ratio.
Receive energy for radiation subsequently as described previously for emitting ions 110, there are at least three kinds of machines
Reason.The most in one embodiment, emitting ions 110 can may directly absorb excitation radiation, and hereafter emitting ions 110
The energy that at least some is absorbed can be given off, typically to compare excitation radiation for different and longer wavelength.At it
In its embodiment, host lattice material 130 or its ion (such as vanadate ion) can may directly absorb excitation radiation,
And transfer energy into emitting ions 110.In another embodiment, host lattice material 130 can comprise one or more
" lattice ion ", it can be launched ion 110 and substitute；With one or more optional sensitized ions, it can absorb excitation
The energy of gained is also transferred to emitting ions 110 by radiation.Host lattice absorption is probably useful in some cases, Bu Guozhu
Lattice absorption is not particularly useful in major part situation.More typically, transition metal ions (such as chromium) or rare earth metal
Ion (such as erbium) is used as sensitized ions.These elements can also serve as emitting ions, or energy can also be turned by they
Moving on to other ion (such as emitting ions 110), then it give off shifted energy.Most host lattice material is all
The absorbent in ultraviolet light range can be served as, because excitation photons energy is the highest in the range of this.But, this phenomenon
May never produce any transmitting coming from combined desired ion.
The lattice ion that can be substituted is the ion in host lattice material 130, its can by one or more sensitizations from
Son (if including) and one or more emitting ions 110 substitute, and are up to and include 100% replacement.100% replacement is rare
See because most of emitting ions far below 100% substitute level time by concentration quenching.But, there is several being worth
The exception noted, wherein specific ion and host lattice combination allow bigger replacement, because the thing of emitting ions in host lattice
Reason separates and is sufficiently far from so that interaction item significantly reduces.
As hereinafter will be explained in greater detail, represent that in phosphor compound 100, the value of the concentration of emitting ions 110 can make
Measure by various embodiments.When this value with the concentration of emitting ions 110 in believable phosphor to using this phosphorescence time corresponding
The article of body can be determined that it is believable.Emitting ions 110 can low-down replacement percentage ratio (e.g., less than 1% mixes
Miscellaneous), medium replacement percentage ratio (such as 1%-20%) or the high percentage ratio (such as 20%-100%) that substitutes substitutes.Such as neodymium (Nd)
Can at most 1.5% relatively low percentage ratio substitute, holmium (Ho) and ytterbium (Yb) can at most 20% moderate percentages replacement, and
Erbium (Er) can at most 60% relatively high percentage ratio substitute, although these and other ion can also replace by different percentage ratio
Generation.Time used herein, term " replacement " expression substitutes with any percentage ratio, including low, medium and high replacement percentage ratio.Replace
Amount for every kind of ion in host lattice material is typically to describe with atomic percent, and wherein host lattice material can be quick
Change and/or the number of ions of emitting ions replacement is equal to 100%.Allow to be sensitized and/or the ion of main material that emitting ions substitutes
Can typically have and size, similar carrying capacity (load) and similar coordination preference as its ionic species that will substitute.By
There may be various position in host lattice, in these positions, the ion in each can be calculated as 100 atomic percents.
Host lattice material 130 comprises wherein combination (such as substituting) emitting ions 110 and the material of optional sensitizer.
More particularly, host lattice material 130 can be form crystal lattice, and different chemical compositions can be in intracell various positions
It is substituted in this form crystal lattice.Host lattice material 130 should select to guarantee that emitting ions 110 can generation can in multiple bands of a spectrum
The transmitting of observation, wherein this transmitting is adapted in use to the embodiment of checking apparatus and method following detailed description of to analyze.?
In various embodiments, host lattice material 130 includes selected from following material: oxide, fluoride, oxysulfide, halogenide,
Borate, silicate, gallate, phosphate, vanadate, oxyhalide, aluminate, molybdate, tungstates, garnet and
Niobates, but other host lattice material can also use.Such as host lattice 130 can include oxygen yttrium sulfide (Y) (Y2O2S or
YOS), yttrium-aluminium-garnet (YAG), gadolinium (Gd) Ga garnet or other material.
In one embodiment, emitting ions 110 includes such ion, and it has in the sub-bands of a spectrum being relatively distant from
Multiple relatively strong transmittings.According to various embodiments, emitting ions 110 includes the ion selected from elements below: chromium (Cr),
Manganese (Mn), cobalt (Co), nickel (Ni), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), terbium (Tb), dysprosium (Dy), holmium (Ho),
Erbium (Er), thulium (Tm) and ytterbium (Yb).Emitting ions 110 can have+trivalent the most in one embodiment, but at other
In embodiment, emitting ions 110 can have different chemical valences (such as+2 and/or+4).
In various embodiments, the total concentration of the emitting ions 110 being substituted in host lattice material 130 be enough to suitably
Phosphor compound is caused to produce detectable transmitting after standing excitation radiation.Such as it is substituted into the transmitting in host lattice material
The total concentration of ion 110 can be that about 0.095 atomic percent is to about 99.995 atomic percents.But can substitute same
Time still produce phosphor compound functional (such as producing the functional of transmitting by being exposed to excitation radiation) send out
The concentration penetrating ion 110 depends on the type of the ion substituted.In other words, the percentage ratio quilt that some ions can be relatively high
Substitute, remain in that the functional of phosphor compound simultaneously, but if other ion is with identical, relatively high percentage ratio
Substituted, then this functional may lose.
The concentration of the emitting ions 110 being substituted in host lattice material 130 should be more than raw-material any background impurities
Level, is simultaneously in and be enough to realize in multiple bands of a spectrum the concentration of desired relationship between emissive porwer.Generally, phosphorescence
The level of body compound REE impurities will be less than a few millionths part (ppm).Although this relatively low impurity level can
The radiance of launching that can cause phosphor compound produces the least change, but described impurity should not result in phosphor
Compounds property produces any significant change.
According to a kind of embodiment, selecting following emitting ions 110, it is by based in phosphor compound 100
The concentration of emitting ions 110 and the branching ratio that changes characterize.In other words, it is in the first concentration when host lattice material 130
Emitting ions 110 when adulterating, phosphor compound 100 will be characterized by the first branching ratio.When host lattice material 130 is located
When the emitting ions 110 of the second different concentration is adulterated, phosphor compound 100 will carry out table by the second different branching ratios
Levy.
After being exposed to excitation radiation, the emitting ions 110 in phosphor compound 100 will launch photon, and considerable
Observe the integrated intensity of transmitting in multiple bands of a spectrum.As will be described in more detail, calculating is compared in one embodiment
Value, which represent relation measured between the integrated intensity in multiple bands of a spectrum, and by this fiducial value and known parameter
(such as desired ratio) compares, and determines that this fiducial value indicates whether that phosphor compound 100 is believable compound.Cause
This, the relationship between integrated emission intensity in multiple bands of a spectrum can serve as certificate parameter.In a kind of embodiment
Middle damping time constant is also used as certificate parameter.
In some cases, emitting ions (one of emitting ions 110 of such as Fig. 1) encourages via direct absorption process,
It includes providing the excitation radiation being in emitting ions absorption band.Selectively, as it was previously stated, host lattice or sensitization from
Son can serve as the approach of excitation emitting ions.In the case of the former, from the transmitting of emitting ions from absorption resonance level
Rapid decay is to storage level.Generally, absorption band is higher than storage level, but the most this situation, and with certainly deposit
The die-away time that water storage is flat is compared, and the die-away time of self-absorption resonant horizontal is the fastest.From storage level, spontaneous photon
Transmitting can occurred by wavelength spectral band determined by storage level and more low energy level.As will be explained in greater detail below
, the feature launching electromagnetic radiation from emitting ions 110 is determined for whether phosphor compound 100 corresponds to
" checking is used " phosphor compound.
Fig. 2-6 shows the various features of phosphor compound, and described compound includes by particular transmission ion (i.e. erbium)
The specific lattice material (i.e. YOS) of doping.It is to be understood that Examples below should not necessarily be construed to restrictive, and these are implemented
Scheme may be used for characterizing other phosphor compound numerous.Although it addition, exemplary phosphor compound includes with specific
The compound (i.e. 2.0,4.0,8.0,16.0 and 32.0 atomic percent) of percentage ratio doping it should be appreciated that these embodiment party
Case can be used for characterizing the phosphor compound with different doping percentage ratio.Including Fig. 2-6, such design is described,
The i.e. branching ratio of phosphor compound is likely to be dependent on the concentration of the emitting ions being substituted in crystal host lattice material.
Fig. 2 is to illustrate according to a kind of embodiment, and emissive porwer (in first wave length) is along with various exemplary phosphor
The doping percentage ratio of compound and the figure that changes.More particularly, Fig. 2 200 depicts the erbium (Er) being in various doping percentage ratios
The YOS of doping transmitting signal level (arbitrary unit (AU)) at 980nm.Point 201 is corresponding to including by about 2.0 atoms hundred
The transmitting signal level of the phosphor compound of the YOS substrate (host) of proportion by subtraction Er ions, point 202 is corresponding to including by about
The transmitting signal level of the phosphor compound of the YOS substrate of 4.0 atomic percent Er ions, point 203 is corresponding to including by greatly
The transmitting signal level of the phosphor compound of the YOS substrate of about 8.0 atomic percent Er ions, point 204 corresponding to include by
The transmitting signal level of the phosphor compound of the YOS substrate of about 16.0 atomic percent Er ions, and point 205 is corresponding to bag
Include the transmitting signal level of the phosphor compound of YOS substrate by about 32.0 atomic percent Er ions.Such as in Fig. 2 200
Shown in, quickly raise (from about 35.0AU to about 120.0AU) from 2.0 to 8.0 foreign atom percentage emissive levels, then
(to about 5.0AU) is will be relatively slowly reduced from 8.0 to 32.0 foreign atom percentage ratios.Actual being relatively typically is carried out as follows
: at some desired wave-length coverage upper integral strength signals, so as to obtain the individual digit with this spectral correlation.This ripple
Long scope generally covers emission band and other bands of a spectrum few, so that any other that may affect result pollutes signal minimum
Change.
Fig. 3 is to illustrate according to a kind of embodiment, and emissive porwer (in second wave length) is along with the exemplary phosphor of Fig. 2
The doping percentage ratio of compound and the figure that changes.More particularly, Fig. 3 300 depicts the Er ions being in various doping percentage ratios
YOS transmitting signal level at 1550nm.Point 301 is corresponding to including by the YOS base of about 2.0 atomic percent Er ions
The transmitting signal level of the phosphor compound of matter, point 302 is corresponding to including by the YOS of about 4.0 atomic percent Er ions
The transmitting signal level of the phosphor compound of substrate, point 303 is corresponding to including by about 8.0 atomic percent Er ions
The transmitting signal level of the phosphor compound of YOS substrate, point 304 is corresponding to including by about 16.0 atomic percent Er ions
The transmitting signal level of phosphor compound of YOS substrate, and point 305 is corresponding to including by about 32.0 atomic percent erbiums
The transmitting signal level of the phosphor compound of the YOS substrate of doping.As shown in Fig. 3 300, from 2.0 to 16.0 foreign atoms
Percentage emissive level quickly raises (from about 18.0AU to about 125.0AU), then from 16.0 to 32.0 foreign atoms hundred
Proportion by subtraction will be relatively slowly reduces (to about 5.0AU).
In Fig. 2 200, in Fig. 3, the analysis of 300 shows that the relation between emissive porwer and doping percentage ratio is for Er ions
It is different under different wavelength for YOS.Such as at 980nm, emissive porwer is at about 8.0 foreign atom percentage ratio (points
203) reach peak value time, and at 1550nm, emissive porwer reaches peak value when about 16.0 foreign atom percentage ratios (point 304).
Because various emitted at wavelengths intensity and doping between relation be nonlinear, therefore the branching ratio between emissive porwer with
The change of doping percentage ratio and change.
Fig. 4 is to illustrate according to a kind of embodiment, ratio the showing along with Fig. 2 of the emissive porwer at the first and second wavelength
The doping percentage ratio of example phosphor compound and the figure that changes.More particularly, Fig. 4 400 depicts for various doping hundred
Proportion by subtraction, the ratio of the emissive porwer at the emissive porwer at 980nm and 1550nm.Point 401 is corresponding to including by about 2.0 atoms hundred
The ratio of the emissive porwer of the phosphor compound of the YOS substrate of proportion by subtraction Er ions, point 402 is former corresponding to including by about 4.0
The ratio of the emissive porwer of the phosphor compound of the YOS substrate of sub-percentage ratio Er ions, point 403 is corresponding to including by about
The ratio of the emissive porwer of the phosphor compound of the YOS substrate of 8.0 atomic percent Er ions, point 404 corresponding to include by
The ratio of the emissive porwer of the phosphor compound of the YOS substrate of about 16.0 atomic percent Er ions, and point 405 corresponds to
Including the ratio by the emissive porwer of the phosphor compound of the YOS substrate of about 32.0 atomic percent Er ions.In Fig. 4
Shown in 400, at relatively low doping percentage ratio, the ratio between integrated emission intensity is of a relatively high (i.e. at 2.0 atomic percent
Be of about 4.0 during the doping percentage ratio of ratio), and this ratio along with the rising of doping percentage ratio steady decrease to relatively low
Value (is i.e. down to about 0.5 when 16.0 atomic percents and higher doping percentage ratio).As will be described in more detail,
Because the ratio between the integrated emission intensity in different bands of a spectrum changes, the most described ratio along with doping percentage ratio
Whether the calculating of (or the another kind of relationship between emissive porwer) can be used to indicate that specific phosphor compound
There is specific doping content, and thus represent whether this specific phosphor compound is believable.Desirably in excitation
After source removes, the same time measures in different bands of a spectrum, because the transmitting in different spectral bands may show substantially
Different attenuation constants.In this case, the function as the time is also changed by integrated emission intensity level.
Although phosphor compound can be described as having transmitting at discrete wavelength (such as 980 or 1550nm) place, but
It is that transmitting relevant to specific wavelength in reality actually spreads all over over a wavelength range (the sub-bands of a spectrum of the most whole spectrum), its
Described in specific wavelength substantially at this band center.Therefore to produce emissive porwer value, signal will be launched at given wavelength
Scope upper integral.In the measurements, this generally uses bandpass filter (band filter) to receive the wave-length coverage of reduction, and
The detector element using the response in the wave-length coverage paid close attention to the most slightly flattened is carried out.Because being likely difficult to compare
Emission peak, therefore can relatively simply measure integrated emission value.As long as the equipment of measurement keeps constant, then the ratio of integrated intensity
Rate should also be stable for given ion substitution amount.Therefore, referenced herein " launching by force at setted wavelength
Degree " or time " intensity ", the integrated intensity measurement result on whole bands of a spectrum can be actually corresponded to.Come more clear with reference to Fig. 5 and 6
Chu ground represents this design.
Fig. 5 is to illustrate according to a kind of embodiment, and emissive porwer is along with the of the exemplary phosphor compound being in Fig. 2
Wavelength in one bands of a spectrum (i.e. center is at the bands of a spectrum of about 980nm) and the figure that changes.As shown in Fig. 5 500, aobvious in the first bands of a spectrum
The transmitting write is present in whole wave-length coverage (the most about 975nm to 1015nm).Track 501 represents and includes by about 2.0
The signal level of the phosphor compound of the YOS substrate of atomic percent Er ions, track 502 expression includes by about 4.0 former
The signal level of the phosphor compound of the YOS substrate of sub-percentage ratio Er ions, track 503 represents and includes by about 8.0 atoms
The signal level of the phosphor compound of the YOS substrate of percentage ratio Er ions, track 504 represents and includes by about 16.0 atoms hundred
The signal level of the phosphor compound of the YOS substrate of proportion by subtraction Er ions, and track 505 represent include by about 32.0 atoms hundred
The signal level of the phosphor compound of the YOS substrate of proportion by subtraction Er ions.
Fig. 6 is to illustrate according to a kind of embodiment, and emissive porwer is along with the of the exemplary phosphor compound being in Fig. 2
Wavelength in two bands of a spectrum (i.e. band center is at the bands of a spectrum of about 1550nm) and the figure that changes.As shown in Fig. 6 600, the first spectrum
Significantly launch in band and be present in whole wave-length coverage (the most about 1500nm to 1610nm).Track 601 represents and includes
By the signal level of the phosphor compound of the YOS substrate of about 2.0 atomic percent Er ions, track 602 represent include by
The signal level of the phosphor compound of the YOS substrate of about 4.0 atomic percent Er ions, track 603 represents and includes by greatly
The signal level of the phosphor compound of the YOS substrate of about 8.0 atomic percent Er ions, track 604 represents and includes by about
The signal level of the phosphor compound of the YOS substrate of 16.0 atomic percent Er ions, and track 605 represent include by about
The signal level of the phosphor compound of the YOS substrate of 32.0 atomic percent Er ions.
Fig. 7 be according to a kind of exemplary for producing phosphor compound (the phosphor chemical combination of such as Fig. 1
Thing 100) the flow chart of method.Generally, people in the art can be used according to the phosphor compound of a kind of embodiment
Any method of the known many conventional methods of member generates.According to a kind of embodiment, the generation of phosphor compound includes
Prepare phosphor host lattice material (the host lattice material 130 of such as Fig. 1) and emitting ions (the one of such as Fig. 1 in block 702
Kind or multiple emitting ions 110) combination form original phosphor compound.In some cases, this can use solid-state
Chemistry realizes.Such as when phosphor compound is oxide phosphor, this can include various oxygen with correct ratio
Compound mixes with the oxide of emitting ions.The time that the mixing of these oxides and roasting (fire) are specified.In other situation
In, it is possible to use solution chemistry technology, wherein various materials are dissolved, with postprecipitation and roasting subsequently.
Depend on the concrete grammar for generating described compound, can be being formed during original phosphor compound
Host lattice material includes other material with the combination of emitting ions.Such as can include each in this original phosphor compound
Plant flux and other precursor.
In square 704, original phosphor compound is carried out post processing, produce light emitting phosphor compound.After such as
Process can include carrying out original phosphor compound any one or more in following process: roasting；Annealing；Suspend；
Precursor removes (such as removing flux)；Grind；Sedimentation；And supersound process.Then the phosphor compound formed can be tied
Close in any article in numerous article so that the benefit of its various characteristics can be realized.Such as, this phosphor compound
Can be incorporated in article to provide a kind of mode verifying these article.
Fig. 8 is the system 800 for checking article 850 according to a kind of exemplary.According to a kind of embodiment party
Case, system 800 includes processing system 802, excitation radiation generator 804, multiple transmitting radiant light detector (" detector ")
806,808 (they have relevant optical filter (light filter) 810,812), optical element 814, data storage 816 and user
Interface 818.Processing system 802 can include one or more processor and relevant circuit, and it is configured to carry out and article
(such as article 850) verify relevant control and the process of analysis (form of the most executable software algorithm).
According to a kind of embodiment, processing system 802 is configured to provide control signal to excitation radiation generator 804,
Its region 852 making excitation radiation generator 804 that excitation radiation 820 to guide article 850 (such as includes phosphor compound
Checking feature should be located therein or region thereon).Desirably, region 852 is corresponding to such region, and it is for credible
Article for include such checking feature, this checking feature be likely to have as one man (consistently) produce and
The believable phosphor material (such as region that state-variable is relatively robust) concentrated.In this control signal, process system
System 802 can specify that provide excitation radiation opportunity (timing) (such as time started, dwell time and/or duration), and/
Or other parameter (such as intensity and/or other parameter) relevant to specific incentives radiation to be generated.Typically, this excitation spoke
The bandwidth penetrated is predetermined based on driving source, and this driving source is included as a part (example of excitation radiation generator 804
The bandwidth of the excitation as produced by selected light emitting diode or laser diode).Various opportunitys and/or radiation occur
Parameter such as can store 816 available from data.Excitation radiation generator 804 can include such as one or more laser instrument, swash
Optical diode, light emitting diode (LED), incandescent filament, lamp or other driving source.
In addition to controlling excitation radiation generator 804, processing system 802 is configured to launching radiation detector 806,
808 provide control input, and it makes transmitting radiation detector 806,808 attempt detection by the region 852 of article 850 as absorption
Response after (directly or indirectly) at least some excitation radiation 820 and the transmitting radiation 822,824,826 that produces.
According to a kind of embodiment, launching radiation 822 irradiation optical element 814, transmitting radiation 822 is separated into first by it
With the second light beam 824,826.First light beam 824 includes the light being in the first bands of a spectrum, and the second light beam 826 includes being in second
Light in bands of a spectrum, the second bands of a spectrum with the first bands of a spectrum overlap, and with the first spectra separating.Optical element 814 is by the first light beam
824 guide a detector 806, and the second light beam 826 is guided another detector 808.According to a kind of embodiment, optics unit
Part 814 is configured to reflect the first light beam 824 and through the second light beam 826.Such as optical element 814 can be selected from following
Element: polychromator, prism, diffraction grating, thin film filter, interference light filter, dichroic (dichroic) light filter, dichroic
Mirror and dichroic reflector.One advantage of this kind of optical element 814 is that it makes both detectors 806,808 to connect simultaneously
Receive the component (components) of the transmitting launched by the same area 852 of article 850, so that the ionization meter of gained
The correlation maximum of result.
Each transmitting radiation detector 806,808 can include such as spectral filter 810,812, one or more electric light
Sensor, photomultiplier tube, avalanche photodide, photodiode, charge coupled device, charge injecting device, take a picture soft
Sheet or other detection device.In a particular embodiment, each transmitting radiation detector 806,808 includes being positioned at article
Spectral filter 810,812 between 850 and photodetector.This spectral filter 810,812 is configured at light beam 824,826
Them are filtered so that only the transmitting in the sub-bands of a spectrum of whole spectrum radiates actually before detector 806,808 is provided to
It is irradiated on the active region of each detector 806,808.Spectral filter 810,812 can include such as growing logical, band is logical or
The other type of optical filter of person, it is configured to only only transmit the light being in paid close attention to bands of a spectrum, and refuse all other
Light.If such as system 800 be configured to checking potentially include phosphor the most aforementioned phosphor example (such as Er ions
YOS) article, then spectral filter 810, one of 812 can include long pass filter (the long pass filter of such as 1500nm), and
And another spectral filter 810,812 can include halfwidth (FWHM) bandpass filter (such as center is at the 20nm of 980nm
FWHM bandpass filter).
Each detector 806,808 has sensitivity in the bands of a spectrum paid close attention to, and therefore can detect and be in this bands of a spectrum
In through spectral filter 810, the light of 812.According to a kind of embodiment, detector 806, one of 808 are configured to detection
Transmitting radiation (such as 980nm or some other bands of a spectrum) being in the first paid close attention to bands of a spectrum, and detector 806, in 808
Another is configured to detect transmitting radiation (such as 1550nm or some other spectrums being in the second paid close attention to bands of a spectrum
Band).Detector 806,808 can be same type or different types of.According to a kind of particular, detector 806,
808 is different types of.Such as detector 806, one of 808 can include silicon detector, and detector 806,808 another can
To include indium-gallium-arsenic (InGaAs) detector (such as telecommunication type or extended pattern InGaAs).In other embodiment
In, it is possible to use other type of detector (the such as vulcanized lead, selenizing of launching radiation in paid close attention to bands of a spectrum can be detected
Lead, germanium, indium antimonide, indium arsenide, platinum silicide, indium antimonide etc.).In a kind of selectable embodiment, it is possible to use single inspection
Surveying device, it can detect the transmitting radiation in all bands of a spectrum paid close attention to.In such a embodiment, optical element 814
Can get rid of from system 800.In other selectable embodiment, it is possible to use more than two detector detects many
The transmitting paid close attention to radiation in two bands of a spectrum.In this kind of embodiment, it is possible to use multiple optical elements are by different
The multiple detector of beam direction.
As it was previously stated, each detector 806,808 creates electronic signal, it is irradiated to detector 806 with collected,
The intensity of the radiation on the active region of 808 is directly proportional.More particularly, each detector 806,808 creates following signal (example
Intensity level as digitized in one or more), this signal represents detector 806,808 received launching the whole of radiation
Integrated intensity on sub-bands of a spectrum.Desirably, when multiple detectors 806,808 are used within the system (such as in the system of Fig. 8
In 800), integrated intensity value is by (the electronically captured) of each detector 806,808 electric fishing collection simultaneously,
Because integrated intensity measurement is likely to produce more steadily and surely and compares accurately simultaneously.Each transmitting radiation detector 806,808
(such as when t=0, each 0.1 millisecond the most behind, for several at the interval that can one or more be pre-selected
Interval) by intensity level digitized.It addition, each transmitting radiation detector 806,808 provides information (such as processing system 802
Digitized intensity level), its spectrum making to launch radiation 822 and time response can be characterized.
Processing system 802 is configured to after receiving this category information be analyzed it, it is therefore an objective to determine whether any institute
Time and the spectral characteristic of the radiation recorded both corresponds to " verify with " phosphor compound and (i.e. has known time and spectrum
The phosphor compound of characteristic, it is used for identifying and/or verifying purpose) time and spectral characteristic.
Will be discussed in greater detail as following, in one embodiment, processing system 802 is configured to calculating and compares
Value, this value represents the first integral intensity launching radiation in the first bands of a spectrum and overlapping with these first bands of a spectrum second
The relationship between the second integral intensity launching radiation in bands of a spectrum.Processing system 802 is configured to determine further
Whether fiducial value is consistent with desired, predetermined certificate parameter (being such as stored in data storage 816), and when this fiducial value
When meeting certificate parameter, it is believable for being accredited as by these article.On the contrary, when this fiducial value does not meets certificate parameter, process system
It is incredible that system 802 is configured to be accredited as article.In a particular embodiment, this fiducial value is that first integral is strong
Spending the ratio between second integral intensity, and described certificate parameter includes such value, it represents for being appointed as
Described in believable article, ratio should fall into ratio ranges therein.In other embodiments, this fiducial value can be based on
The different calculated value of relationship between first and second integrated intensities.In other embodiments more, should
Fiducial value can be based on the actual strength meter removing or closing the regulation moment after driving source (such as launching radiation 822)
The value obtained.Signal in respective wavelength scope is entered by the combination of each optical filter 810,812 and detector 806,808
Row integration.After removing or closing driving source, then described intensity level reduces due to the attenuation properties of transmitting.If system
The measurement time of 800 keeps fixing, then the strength ratio of authentic material should keep relative constancy.
It addition, in one embodiment, processing system 802 may determine that the time response of measured radiation whether with
Other predetermined certificate parameter is consistent.Such as when processing system 802 may determine that whether the die-away time launching radiation is with decay
Between parameter be consistent.When not meeting parameter die-away time this die-away time, it is not that these article can be accredited as by processing system 802
Believable.
Pre-corresponding to desired by checking phosphor compound really when time of measured radiation and spectral characteristic
During fixed certificate parameter, processing system 802 can take some to be accredited as, to by article 850, the action that credible article are relevant.Such as
Processing system 802 can transmit a signal to user interface 818, and it makes user interface 818 produce the perceptible credibility of user to refer to
Show (labelling that such as shows, light, sound etc.), and/or processing system 802 can make transmission (routing) assembly of system 800 (not
Illustrate) article 850 are sent towards the path or receptor (bin) being entered as credible article.Selectively, when measured
During the desired predetermined certificate parameter of time of radiation and/or spectral characteristic the most corresponding checking phosphor compound, locate
Reason system 802 can take some to be accredited as, to by article 850, the action that insincere article are relevant.Such as processing system 802 is permissible
Transmit a signal to user interface 818, its make user interface 818 produce user's perceptible insincere property instruction (such as show
Labelling, light, sound etc.), and/or processing system 802 can make the sending assembly (not shown) of system 800 by article 850 towards assignment
Path or receptor for insincere article send.
User interface 818 can include that the random component in numerous assembly, described assembly can be provided by user operation
To the input (such as keyboard, button, touch screen etc.) of system 800, or can be processed system 802 control produce user can
The instruction (such as display screen, light, speaker etc.) discovered.Said process can respond the input of user and start, and this user is defeated
Entering e.g. is provided by the interaction of user Yu user interface 818.Selectively, said process can by system 800 certainly
Dynamic start, such as when article 850 be placed in can carry out the position encouraging and detecting process time.
Fig. 9 is the flow chart of a kind of method for carrying out item authentication according to exemplary, and these article can
Phosphor compound can be included.The such as embodiment of method shown in Fig. 9 can be by checking system (the checking system of such as Fig. 8
System 800) carry out.In square 902, when article (article 850 of such as Fig. 8) to be verified are verified system reception, should
Process can start.Such as these article can be placed manually in the suitable receiving portion of checking system, or these article can
To be automatically sent in receiving portion (such as by sorting or transmitter system).
In square 904, article are made to be exposed to excitation radiation.Such as article can be moved to energized position (such as exist
Under excitation window), and processing system (processing system 802 of such as Fig. 8) can be to (the excitation of such as Fig. 8 of excitation radiation generator
Radiation generator 804) send control signal, it causes excitation radiation generator that excitation radiation guides described article.Optional
Ground, excitation radiation generator can provide adjustable excitation radiation or excitation radiation continuously.
In square 906, stop providing excitation radiation to article.This can be by closing excitation radiation (the most wherein
Article can keep in fixing and that excitation radiation is impulse type system) complete, or by article are moved apart excitation radiation
Guide region therein and move to detect position (such as detection window under) and complete.In a kind of selectable embodiment
In, excitation radiation can provide continuously, and the most described system carries out following detection process.
In square 908, the detection of checking system radiates (such as by figure from the transmitting being in multiple bands of a spectrum of article
The transmitting radiation detector 806,808 of 8).Detection can be carried out with one or more assay intervals, and described interval is that self-stopping technology will
Excitation radiation guides the measure of time of article.According to a kind of embodiment, described system is configured to detection at the first bands of a spectrum
Radiate with the transmitting in the second bands of a spectrum, but this system can also be configured to detection transmitting spoke in more than two bands of a spectrum
Penetrate.
In square 910, analyze the strength information launching radiation quantified measured by multiple bands of a spectrum and (such as pass through
The processing system 802 of Fig. 8).In one embodiment, the mathematics between the intensity launching radiation in multiple bands of a spectrum is calculated
Relational expression.In a particular embodiment, this relationship is ratio, and fiducial value C can calculate according to following:
C = IB1/ IB2, (formula 1)
Wherein IB1Represent in the first bands of a spectrum measure integrated emission intensity (or remove excitation after predetermined instant institute
The absolute intensity measured), and IB2Represent integrated emission intensity (or predetermined after removing excitation measured in the second bands of a spectrum
Absolute intensity measured by moment).
In other embodiments, this fiducial value can be detected many based on the multiple moment after stopping excitation radiation
Individual transmitting radiant intensity determines.Such as can calculate the mean intensity of each bands of a spectrum, and fiducial value can be mean intensity
Ratio.Selectively, the ratio of intensity in each bands of a spectrum can be calculated in multiple detection moment, and this fiducial value is permissible
It it is average ratio.In other embodiments, it is possible to use other relationship, it includes multiple intensity measurements conduct
Variable.Selected relationship can depend on the emission characteristics of phosphor compound to be verified, and other factors.Example
As for specific phosphor compound, if launching in bands of a spectrum is the fastest compared with the transmitting in another bands of a spectrum
Ground decay (such as this transmitting has little time constant), then the ratio between intensity can have in molecule (numerator)
There is the value of the transmitting characterizing this rapid decay, to avoid this ratio quickly to increase on little incremental time.Implement according to one
Scheme, can set the acquisition value (gains) of detecting system (system 800 of such as Fig. 8), so that desired ratio is set
For single (unity) (or some other desired values).In this kind of embodiment, the change of ratio can be relatively easily
Detect, and little measurement error is not result in big deviation.
According to a kind of embodiment, the analysis launching radiation can also include determining the transmitting in one or more bands of a spectrum
The die-away time of radiation.In one embodiment, described die-away time can be based at multiple moment (such as t=0, t=0.1
Millisecond etc.) measured by launch radiation intensity determine.By removing excitation radiation, emissive porwer changes over and decays
And the rate of decay of emitting ions can be characterized by damping time constant.Such as index simple in emissive porwer is declined
Subtracting, damping time constant can be represented by the constant, τ in following formula:
I(t)= I0e-t/ τ, (formula 2)
Wherein t express time, I (t) represents the emissive porwer at moment t, and I0Represent emissive porwer (the such as t at t=0
=0 can correspond to stop providing moment during excitation radiation).Although the emissive porwer of some phosphor compound can basis
Simple exponential decay above, but the emissive porwer of other phosphor compound may be by multiple exponential dampinies
Impact (such as when there is the mechanism of multiple impact decay).In some cases, phosphor compound may not show letter
Single single exponent ring-down, particularly all the more so when energy transfer is this mechanism a part of.
In square 912, described fiducial value is compared with one or more certificate parameters.Such as certificate parameter is permissible
Including lower limit, the upper limit, scope etc..More particularly, the scope of the ratio of the emissive porwer in fiducial value is the first and second bands of a spectrum
Embodiment in, certificate parameter can include define ratio ranges upper and lower bound.In this kind of situation, fiducial value with test
A kind of comparative result that card parameter is consistent is that the ratio (fiducial value calculated by square 908) of wherein emissive porwer falls into this ratio
In the range of (the most described ratio more than lower limit and be less than the upper limit).On the contrary, the one that fiducial value does not corresponds with certificate parameter compares knot
Fruit is that the ratio of emissive porwer is less than lower limit or more than the upper limit.In addition to assessment fiducial value, for specific phosphor chemical combination
Thing, it is also possible to determine whether die-away time is in the range of regulation.
In square 914, when determining fiducial value and meeting certificate parameter, (with optionally, damping time constant meets can
During scope die-away time accepted), it is " believable " and can take in square 914 that article can be accredited as by this system
Corresponding action.Such as this system can produce the instruction of the perceptible credibility of user, and/or can make the transmission group of system
Article are sent by part towards the path or receptor being entered as credible article.Selectively, it is not inconsistent when determining this fiducial value
During conjunction certificate parameter (or optionally, when this damping time constant does not meets acceptable scope die-away time), this system can
It is " incredible " corresponding action can be used in square 918 so that article are accredited as.Such as this system can produce
The instruction of the perceptible insincere property of user, and/or the sending assembly of system can be made towards be entered as can not keepsake by article
The path of product or receptor send.
Figure 10 shows the sectional view of the article 1000 according to a kind of exemplary, and it includes the material of phosphor-containing
Material.A kind of embodiment of such as article 1000 can include embed and/or the checking feature 1010,1020 of surface applied
And/or article 1000 can include that phosphor particles 1030, described granule are evenly or unevenly dispersed in article 1000
In one or more assemblies (such as in base material 1002 and/or in one or more layers of article or other assembly).Checking
The various relative sizes of feature 1010,1020 and granule 1030 can not be drawn to scale in Fig. 10.Although article
1000 are illustrated as including that embed and surface applied checking feature 1010, with granule 1030 both 1020, but other one
Plant one of article checking feature, the checking feature of surface applied and the scattered phosphor particles that can include embedding or group
Close.Finally, although Figure 10 only show the checking feature 1010 of embedding, 1020 each one, but article can comprise more than
One any type of checking feature 1010,1020.
Article 1000 include base material 1002, and it can be rigidity or flexibility, and in various embodiments its
Can be formed by one or more layers or assembly.The various structures of base material 1002 are large number of and are difficult to address one by one, because
The phosphor compound of various embodiments can be used together with numerous different types of article.So, although Figure 10 schemes
Show simple single base material 1002 it should be appreciated that base material 1002 can have any configuration in numerous different configuration.
Although it addition, the most only discuss solid article it should be appreciated that " article " can also include people, animal, biological specimen,
Other of fluid sample and the substantially any phosphor compound that can include a kind of embodiment wherein or thereon
Object or material.
The checking feature 1010 embedded comprises one or more rigidity or flexible material, includes wherein or thereon
A kind of phosphor compound of embodiment.The checking feature 1010 such as embedded can be configured to discrete rigidity or flexibility
Base material, safety line or the form of another type of structure.According to various embodiments, the checking feature 1010 of embedding can have
There is scope to be of about 1 micron of thickness 1012 until the thickness 1004 of base material 1002, and the checking feature 1010 embedded is permissible
There is such width and length, its width being less than or equal to base material 1002 and length.
Checking feature that the checking feature 1020 of surface applied can e.g. be printed or include one or more rigidity
Or the checking feature of flexible material, include the phosphor compound of a kind of embodiment within this material or thereon.Example
The ink of aforementioned phosphor compound, pigment, coating or oil is included as the checking feature 1020 of this surface applied can comprise
Paint.Selectively, the checking feature 1020 of this surface applied can comprise one or more and includes wherein or thereon
The rigidity of phosphor compound or flexible material, wherein then this base material adheres to or is otherwise attached to article base material
On the surface of 1002.According to various embodiments, the checking feature 1020 of surface applied can have about 1 micron or higher
Thickness 1022, and the checking feature 1020 of surface applied can have the width of the width less than or equal to base material 1002 and length
Degree and length.
Phosphor particles 1030 can be evenly or uniformly dispersed in base material 1002, as shown in Figure 10, or at it
Its embodiment is dispersed in other assemblies one or more of article 1000 (such as article one or more layers or
In other assembly).In phosphor particles 1030 can be dispersed in base material 1002 or in another assembly, such as by by granule
In 1030 basic materials being attached to base material 1002 or other assembly (such as paper pulp, plastics base resin etc.) and/or by use
The aqueous colloidal dispersion immersed substrate 1002 of granule 1030 or other assembly.Dipping can such as be dripped by printing, pouring
Or spraying method is carried out (dripping).In one embodiment, the granularity of phosphor particles 1030 can be 1 micron
To 20 microns, but phosphor particles 1030 might be less that or is more than range given above.
In various embodiments, article 1000 can be any kind of article, and it is selected from including but not limited to identity
Card, driving license, passport, identification document, banknote, check, file, paper, stock, package component, the credit card, bank card, label, envelope
The group of bar, stamp, liquid, people, animal and biological sample.Base material 1002 can be any base material in all kinds of base material, and wraps
Including one or more following materials, it is selected from including but not limited to paper, polymer, glass, metal, textile and fiber
Group.
For verifying light emitting phosphor compound and being combined with their the various embodiments of method and apparatus of article
Have been described above.Described method and apparatus can be used therewith the embodiment bag of phosphor compound
Include the adulterant (emitting ions such as substituted) characterized by the sub-bands of a spectrum of multiple transmittings.Desirably, doping content can be at phosphorus
Body of light growth course is well controlled, to produce stable ratio between the sub-bands of a spectrum of transmitting.According to a kind of embodiment party
Case, multiple spectral emissions are relatively distant from so that different types of detector may be used for each spectrum that detection is paid close attention to
Launch.This kind of embodiment can help to produce relatively robust checking phosphor compound, because the detector of routine can
The compound with different emitting ions concentration can be cannot be distinguished by.So, it is intended to generate and there is secret
(confidential) phosphor compound of doping content would be impossible to successfully.It addition, because growing method may be notable
Affecting damping time constant, growth course is likely to affect ratio reading.This means the dopant level meeting of not only secret
Strengthen the robustness of phosphor compound, and use the growth of the growth course being different from good that control and/or secret
Cheng Buneng produces the phosphor compound that can produce same ratio reading.
When a kind of embodiment of phosphor compound is included in carrier such as containing time in chromophoric ink, this ink
Absorbance is likely to change the ratio of signal, and the effect of ink can take in proof procedure.When phosphor
When compound is included in paper or other medium, similar effect is likely to occur.
The advantage of various embodiments is that described production method (and quality guarantee relevant to the method) may produce
Having the phosphor compound of following transmitting ratio, this transmitting ratio there is no the production method about described phosphor compound
It is difficult to during with the details of composition.As detailed above, use the single emitting ions of predetermined concentration to produce
Give birth to predictable emissive porwer ratio.Described method is also sane (the robust to of single order to hybrid variable and particle size distribution
first order).On the contrary, dimorphism labelled reagent (taggant) system is significantly more susceptible to error occur.
It addition, according to a kind of embodiment, use the component analysis of single driving source and single transmitting light beam to provide more
Sane checking, because energy flows through electronics collector in uniform and reproducible mode.This can substantially eliminate owing to changing
Become the stimulation level in described source and error that spectral shift causes.These error aspects have only resulted in the change of signal magnitude,
And it is eliminated by signal ratio method.
Although having been presented at least one exemplary embodiment in detailed description above it should be appreciated that
There is numerous variant.It should also be understood that the one or more exemplary be only citing, be not intended to
Any mode limits the scope of present subject matter, applicability or structure.On the contrary, aforementioned detailed description will be for art technology
Personnel provide convenient route map, implement the exemplary of the present invention, it should be understood that can be exemplary embodiment party
Element function described in case and carry out various change in arranging, without deviating from the present invention defined in claims and it
The scope of legal equivalents.
Claims (19)
1., for the method for checking article, described method comprises the steps:
The certain area making described article is exposed to excitation radiation；
Detect from region described in these article be in the first bands of a spectrum and be in overlapping with described first bands of a spectrum second
Transmitting radiation in bands of a spectrum, wherein said first bands of a spectrum are corresponding to the first sub-bands of a spectrum of transmitting of emitting ions, and described second spectrum
Band is corresponding to the second sub-bands of a spectrum of transmitting of described emitting ions；
Calculate fiducial value, this value represent be in the first bands of a spectrum launch radiation the first intensity be in the second bands of a spectrum
Launch the relationship between the second intensity of radiation；And
Determine whether described fiducial value is consistent with certificate parameter；
Wherein said first bands of a spectrum and described second bands of a spectrum are being substituted into selected from following host lattice material corresponding to single ionic
Emission band after Nei: oxide, fluoride, oxysulfide, halogenide, borate, silicate, gallate, phosphoric acid
Salt, vanadate, oxyhalide, aluminate, molybdate, tungstates, garnet and niobates；
Wherein said single ionic is selected from following element: neodymium, holmium and erbium；
Wherein neodymium can the relatively low percentage ratio of at most 1.5 atom % substitute, and holmium can the medium percentage of at most 20 atom %
Than substituting, and erbium can the relatively high percentage ratio of at most 60 atom % substitute,
The number of ions that wherein host lattice material can be substituted is equal to 100 atom %.
2. the method for checking article of claim 1, wherein said first intensity is that the first integral in the first bands of a spectrum is strong
Degree, and described second intensity is the second integral intensity in the second bands of a spectrum.
3. the method for checking article of claim 1, it farther includes after exposure step:
Stop providing excitation radiation in the first moment, after stopping providing excitation radiation, wherein carry out the described inspection launching radiation
Survey.
4. the method for checking article of claim 3, wherein said first intensity is the pre-timing after the first moment
Carve the first absolute intensity measured, and described second intensity be predetermined instant after the first moment measure second the strongest
Degree.
5. the method for checking article of claim 1, wherein said first bands of a spectrum and described second bands of a spectrum are corresponding to single
Ion emission band after being substituted in following host lattice material: oxygen yttrium sulfide, yttrium-aluminium-garnet and gadolinium gallium stone
Garnet.
6. the method for checking article of claim 1, wherein detects described transmitting radiation and comprises the steps:
Described transmitting radiation is separated into the first light beam and the second light beam, and described first light beam includes being in the first bands of a spectrum
Light, and described second light beam includes the light that is in the second bands of a spectrum；
Detect the first intensity from the first light beam；With
Detect the second intensity from the second light beam.
7. the method for checking article of claim 1, wherein detects described transmitting radiation and comprises the steps:
Described transmitting radiation is separated into the first light beam and the second light beam, and described first light beam includes being in the first bands of a spectrum
Light, and described second light beam includes the light that is in the second bands of a spectrum；
With the first light beam described in the first filter filters to produce the light beam of the first filtration；
With the second light beam described in the second filter filters to produce the light beam of the second filtration；
Detect the first intensity from the first light beam filtered；With
Detect the second intensity from the second light beam filtered.
8. the method for checking article of claim 1, wherein calculates described fiducial value and comprises the steps:
Calculating the ratio between the first intensity and the second intensity, wherein said fiducial value is this ratio.
9. the method for checking article of claim 1, wherein determines that whether described fiducial value is consistent with certificate parameter and includes
Following steps:
Determine whether described fiducial value falls into by lower limit and upper limit limited range；
When described fiducial value fall into described in the range of time, it is determined that described fiducial value meets certificate parameter, and wherein said method is entered
One step includes that it is believable for being accredited as by described article；With
When described fiducial value falls when described scope is outer, it is determined that described fiducial value does not meets certificate parameter, wherein said method
It is incredible for farther including to be accredited as described article.
10. the method for checking article of claim 1, it farther includes following steps:
Determine whether the described die-away time launching radiation is consistent with parameter die-away time；With
When not meeting described parameter die-away time described die-away time, it is incredible for being accredited as by described article.
The method for checking article of 11. claim 1, it farther includes following steps:
When described fiducial value does not meets described certificate parameter, it is incredible for being accredited as by described article.
12. equipment being used for checking article, described equipment comprises:
Excitation radiation generator, its certain area being configured to excitation radiation guides article；
First launches radiation detector, and it is configured to detect the transmitting being in the first bands of a spectrum from region described in these article
Radiation, wherein said first bands of a spectrum are corresponding to the first sub-bands of a spectrum of transmitting of emitting ions；
Second launches radiation detector, and it is configured to detect and does not overlap with the first bands of a spectrum from being in of region described in these article
The second bands of a spectrum in transmitting radiation, wherein said second bands of a spectrum corresponding to described emitting ions second transmitting sub-bands of a spectrum；With
Processing system, its be configured to calculate fiducial value, this value represent be in the first bands of a spectrum launch radiation the last the first
Relationship between degree and the second intensity launching radiation being in the second bands of a spectrum, with determine described fiducial value whether with
Certificate parameter is consistent；
Wherein said first bands of a spectrum and described second bands of a spectrum are being substituted into selected from following host lattice material corresponding to single ionic
Emission band after Nei: oxide, fluoride, oxysulfide, halogenide, borate, silicate, gallate, phosphoric acid
Salt, vanadate, oxyhalide, aluminate, molybdate, tungstates, garnet and niobates；
Wherein said single ionic is selected from following element: neodymium, holmium and erbium；
Wherein neodymium can the relatively low percentage ratio of at most 1.5 atom % substitute, and holmium can the medium percentage of at most 20 atom %
Than substituting, and erbium can the relatively high percentage ratio of at most 60 atom % substitute,
The number of ions that wherein host lattice material can be substituted is equal to 100 atom %.
The equipment for checking article of 13. claim 12, wherein said processing system is configured to by calculating the last the first
Ratio between degree and the second intensity calculates described fiducial value, and wherein this fiducial value is described ratio.
The equipment for checking article of 14. claim 12, wherein said first transmitting radiation detector and described second
Penetrate radiation detector and include different types of detector.
The equipment for checking article of 15. claim 12, also includes:
Optical element, it is configured to described transmitting radiation is separated into the first light beam and the second light beam, and the first light beam includes place
Light in the first bands of a spectrum and the second light beam include the light being in the second bands of a spectrum, and wherein the first light beam is directed to described first
Penetrate radiation detector and the second light beam is directed to described second and launches radiation detector.
The equipment for checking article of 16. claim 15, wherein said optical element is configured to reflect the first light beam also
Through the second light beam.
The equipment for checking article of 17. claim 15, wherein said optical element is selected from following element: polychrome
Instrument, prism, diffraction grating, thin film filter, interference light filter, dichroic filter, dichroic mirror and dichroic reflector.
The equipment for checking article of 18. claim 15, also includes:
First optical filter, it was configured to before the first light beam provides the first transmitting radiation detector filter the first light
Bundle；With
Second optical filter, it was configured to before the second light beam provides the second transmitting radiation detector filter the second light
Bundle.
The equipment for checking article of 19. claim 12, wherein said first and second launch radiation detector includes one
Individual or multiple selected from following detector: silicon detector and indium-gallium-arsenic detector.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161508302P | 2011-07-15 | 2011-07-15 | |
| US61/508302 | 2011-07-15 | ||
| US61/508,302 | 2011-07-15 | ||
| US13/537,414 US9239262B2 (en) | 2011-07-15 | 2012-06-29 | Methods and apparatus for authenticating articles with luminescent phosphor compounds |
| US13/537,414 | 2012-06-29 | ||
| US13/537414 | 2012-06-29 | ||
| PCT/US2012/046379 WO2013012655A1 (en) | 2011-07-15 | 2012-07-12 | Methods and apparatus for authenticating articles with luminescent phosphor compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103649729A CN103649729A (en) | 2014-03-19 |
| CN103649729B true CN103649729B (en) | 2016-11-30 |
Family
ID=
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101044536A (en) * | 2004-07-19 | 2007-09-26 | 霍尼韦尔国际公司 | Security taggents in adhesive plastic film laminate for pharmaceutical packaging |
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101044536A (en) * | 2004-07-19 | 2007-09-26 | 霍尼韦尔国际公司 | Security taggents in adhesive plastic film laminate for pharmaceutical packaging |
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