Throughout the following detailed description similar reference characters refer to similar elements in all figures of the drawings. Although the present apparatus is described in the context of utilizing a blue or near ultraviolet excitation source and detecting longer wavelength visible luminescence (i.e., a so-called down-conversion mode), it should be appreciated the principles described apply equally to other excitation wavelengths and to other luminescence wavelengths. Luminescent materials emitting at shorter wavelengths than the excitation source are also contemplated as being within the scope of application of the present apparatus. In such an instance the apparatus of the present invention could be operated in an upconversion mode by (for example) replacing the 400 nanometer LED excitation source with a near infrared emitting LED or laser LED, and using filters appropriate for the upconverted wavelengths from the security mark. Typical upconverting phosphors could be used, for example Y2O2S:Yb, Er, in which case the band-pass filters (or notch filters) would be selected to pass (or reflect) the luminescence wavelengths associated with Er, and the excitation of 980 nanometers would stimulate the upconversion process via excitation of Yb ions followed by energy transfer to Er. The excitation source would still be modulated (as for down conversion) at a frequency consistent with the Er luminescence lifetime.
An example of an emission spectrum of a commercially available luminescent material is shown in
The optical arrangement 15 is comprised of an illumination assembly 20 and a luminescence detector unit 40. The luminescence detector unit 40 may comprise a plurality of photodetector assemblies 50, 60, . . . , 90. The number of photodetector assemblies is chosen according to the number of wavelength bands of emission from the luminescent material.
The illumination assembly 20 is comprised of a light source 22, energized by an associated driver circuit 220, a band-pass filter 24, a collimating lens 26, a wavelength-selective beam splitter 28 and a focusing lens 30. The light source 22 is typically a light emitting diode (LED) operating in the blue or near ultraviolet portion of the light spectrum and is chosen in accordance with the absorption spectrum of the luminescent material to be illuminated. Other possible light sources include laser LEDs, tungsten lamps, quartz halogen lamps, mercury (Hg) lamps, xenon (Xe) lamps, and solid state lasers.
The filter 24 is employed to limit the range of wavelengths of the excitation illumination. If the emission of the light source 22 is sufficiently narrow, filter 24 may be omitted. The response of the filter 24 is selected to match a known absorption band of the luminescent material in the security mark. The filter 24 might typically be a narrow band-pass filter, but filters having other response functions might be employed.
Light from the LED 22 that has passed through the filter 24 is collected by the collimating lens 26 that substantially collimates the light beam. An SF-5 antireflective coated plano-convex f1 lens (available as Edmund Optics part number P45-504) has been found suitable as lens 26. The substantially collimated light is directed to the wavelength-selective beam splitter 28 that reflects the illumination beam along an optical axis A (the axis segment A1). The beam splitter 28 is typically a wavelength-specific beam splitter that reflects most of the blue light from the LED 22 that has passed through filter 24 and transmits a small amount of the blue light and most of the other longer wavelengths, such as green or red light. The light reflected by beam splitter 28 is directed along the primary axis segment A1 to the focusing lens 30 that focuses the illumination beam on the security mark 12. The focusing lens 30 is typically an f/1 plano-convex lens (such as Edmund Optics part number P45-504). The light emitted by the security mark 12 is primarily luminescence from luminescent materials within the security mark 12 and has a wavelength spectrum different from that of the excitation illumination beam.
This light emitted by the security mark 12 is collected and substantially collimated by the lens 30, and directed back along the optical axis segment A1 in a substantially collimated manner. This substantially collimated light passes through the wavelength-specific beam splitter 28 and along the primary axis (the segment A2) to a series of photodetector assemblies 50, 60, . . . , 90. An optional filter 34 may be used to block stray light from reaching the photodetector assemblies.
Each photodetector assembly comprises an optical divider (48, 58, . . . , 88 respectively) positioned along the primary axis A, a lens (52, 62, . . . , 92 respectively), a narrow band-pass filter (54, 64, . . . , 94 respectively), and a photodetector (46, 56, . . . , 96 respectively) positioned along secondary axes A3, A5, . . . , AN-1, respectively. A photodetector assembly 100, comprising a lens 102, a narrow band-pass filter 104 and a photodetector 106 is positioned along axis segment AN.
The optical divider may be implemented in one of several forms: as a non-wavelength-selective beam splitter, as a wavelength-selective beam splitter, or as a special form of wavelength-selective beam splitter known as a notch or Rugate filter. A description of notch and Rugate filters, is found in Thin-Film Optical Filters by H. A. Macleod, Institute of Physics Publishing, Philadelphia, third edition (2001). The following discussion assumes the optical divider is implemented as a non-wavelength-selective beam splitter.
The photodetectors 56, 66, 76, . . . , 106 may be silicon photodiodes, avalanche silicon photodiodes, photomultipliers, or charge-coupled devices (CCDs), although silicon photodiodes, such as a model UDT-555D available from UDT Sensors, Inc., Hawthorne, Calif. or a model S1337-66BR Si Photodiode Detector—5.8 mm, from Hamamatsu Corporation, Bridgewater, N.J. are preferred.
The optical divider 48 of photodetector assembly 50 causes a first portion (typically about 20-30%) of the incident light to be reflected along a secondary axis segment A3, while a second portion (typically about 70-80%) passes through the optical divider 48 and travels along primary axis segment A4. Light directed along the secondary axis segment A3 is focused by a lens 52, passes through a band-pass filter 54, and is detected by a photodetector 56. The photodetector 56 and associated preamplifier 56P creates an electrical signal representation of the light intensity incident on photodetector 56 which is transmitted to the signal processing assembly 250. A first so-called wavelength band of interest of the luminescence emission is thus detected by photodetector assembly 50.
Light traveling along primary axis segment A4 is directed to a photodetector assembly 60. The optical divider 58 of photodetector assembly 60 reflects a portion of the incident light (typically about 30-50%) along a secondary axis segment A5 and transmits the remaining portion along primary axis segment A6. Light directed along the secondary axis segment A5 is focused by a lens 62, passes through a band-pass filter 64, and is detected by a photodetector 66. The photodetector 66 and associated preamplifier 66P creates an electrical signal representation of the light intensity incident on photodetector 66 which is transmitted to the signal processing assembly 260. The photodetector 66 is also typically a model UDT-555D silicon photodiode as described above. A second wavelength band of interest of the luminescence emission is thus detected by photodetector assembly 60.
Light traveling along primary axis segments A6, . . . , AN is detected by subsequent photodetector assemblies 70, . . . , 100. Each subsequent photodetector assembly 70, . . . , 100 is similar to the previously described photodetector assemblies 50, 60. The reflectivities of each optical divider 48, 58, . . . , 88 is selected in accordance with the total number of photodetector assemblies 50, 60, . . . , 100 employed in the apparatus. It may be appreciated that the optical divider 48, 58, . . . , 88 divide the luminescence emanating from security mark approximately equally and direct the luminescence light to the photodetector assemblies 50, 60, . . . , 100 at approximately equal intensities.
The light emitted by the security mark 12 is collected and substantially collimated by the lens 30, and directed back along the primary optical axis segment A1 in a substantially collimated manner. This substantially collimated luminescence passes through the wavelength-specific beam splitter 28, through the optional filter 34 and along the primary axis (the segment A2) to a series of photodetector assemblies 50′, 60′, 70′. Each photodetector assembly 50′, 60′ comprises an optical divider (48′ or 48″, 58′ or 58″ respectively), each positioned along the primary axis A, a lens (52′, 62′ respectively), a narrow band-pass filter (54′, 64′ respectively), and a photodetector (46′, 56′ respectively) positioned along secondary axes A3, A5 respectively. A photodetector assembly 70′, comprising a lens 72′, a narrow band-pass filter 74′ and a photodetector 66 is positioned along primary axis segment A6.
The (non wavelength-selective) optical divider 48′ causes a first portion (typically about 30%) of the incident light to be reflected along a secondary axis segment A3, while a second portion (typically about 70%) passes through the beam splitter 48′ and travels along primary axis segment A4. Light directed along secondary axis segment A3 is focused by a lens 52, passes through a band-pass filter 54, and is detected by a photodetector 56. The photodetector 56 and associated preamplifier 56P creates an electrical signal representation of the light intensity incident on photodetector 56 which is transmitted to the signal processing assembly 250. Light traveling along primary axis segment A4 is directed to an optical divider 58′. The optical divider 58′ reflects a portion of the incident light (typically about 50%) along axis segment A5 and transmits the remaining portion along primary axis segment A6. Light directed along secondary axis segment A5 is focused by a lens 62, passes through a band-pass filter 64, and is detected by a photodetector 66. The photodetector 66 and associated preamplifier 66P creates an electrical signal representation of the light intensity incident on photodetector 66 which is transmitted to the signal processing assembly 250.
Light traveling along primary axis segment A6 is detected by subsequent photodetector assembly 70, comprising a lens 72, a band-pass filter 74 and a photodetector 76 and associated preamplifier 76P. The reflectivities of each beamsplitter 48′, 58′ is selected to divide the luminescence emanating from security mark 12 approximately equally and to direct the luminescence light to the photodetector assemblies 50, 60, 70 at approximately equal intensities.
If expected luminescence wavelength bands are closely spaced, as is the case for some luminescent materials having luminescence peaks spaced only 20-30 nanometers apart, the optical dividers 48 and 58 are typically chosen to be non wavelength-selective optical dividers (e.g., broadband beam splitters) that partially reflect and partially transmit light substantially equally at all wavelengths. The narrow band-pass filters 54, 64 then permit only the expected narrow wavelength bands of luminescence to reach the respective photodetector assemblies 50 and 60. If these expected wavelength bands are sufficiently separated in wavelength, such as might be expected if the security marks contain two different rare earth ions, such as europium (Eu) and terbium (Tb), then wavelength-selective beam splitters 48″ and 58″ might be employed (in place of beam splitters 48′ and 58′, which are not wavelength-selective) without the need for the narrow band-pass filters 54, 64. The use of wavelength-selective beam splitters has the potential to increase the optical intensities at the respective photodetector assemblies 50, 60 and 70 by several-fold.
It should be noted that it is important that the transmission characteristics of the band-pass filters closely match the spectral peak (i.e., the wavelength bands of interest) to be detected or match the wavelength range where the absence of light energy is expected.
An apparatus 10 having an arrangement in accordance with
A series of “Tb3++Eu3+” luminescence spectra were “synthesized” by mathematically adding a first spectrum (
The filter transmission spectra were measured at a 45 degree angle of incidence using a Perkin-Elmer Lambda 9000 UV-visible-near infrared spectrometer with 1 nanometer resolution and 1 nanometer step sizes and the reflectivity spectrum was calculated using the equation: R (reflectivity)=1−T (transmission) (i.e. assuming no absorption is present). The filter reflectivity spectra of the “green” and “red” filters are respectively shown in
An apparatus in accordance with
As seen in
In operation, the timing and control unit 210 generates a timing reference signal that is transmitted to the driver unit 220 and to the signal processor assembly 230. The driver unit 220 generates a series of pulses each having a predetermined time duration and each spaced at predetermined time intervals to drive the light source 22. The predetermined time duration is selected in accordance with the luminescence characteristics of the luminescent material, e.g., excitation time to reach full luminescence. The predetermined time interval between pulses is selected in accordance with the luminescence decay characteristics of the luminescent material, e.g., the time for luminescence to decay to a negligible level. For each pulse of light from source 22 the signal processor channel 240 samples the signal from the monitoring photodetector 32, its associated A/D converter converts the signal to a digital value and the value is stored in an row array 240A in memory 230M. Thus each value stored in array 240A represents the light intensity for a specific pulse of light from the light source. This value may optionally be used later to normalize the detected signals from the photodetector assemblies 50, 60, . . . , 90, 100.
After a predetermined time delay (sufficiently long to allow fluorescence of the substrate to decay to negligible levels) each signal processing channel 250, 260, . . . , 290, 300 starts sampling the output of its respective photodetector. A plurality of samples are converted to digital values by the respective A/D converters and the values are stored in the memory 230M. The values are stored in memory arrays 250A, 260A, . . . , 290A, 300A, each array corresponding to each processor channel 250, 260, . . . , 290, 300. Each column of an array represents the luminescence response of a photodetector to a single excitation pulse and each row of that array represents a sample at a predetermined time after the timing pulse. A separate array is stored for each channel of the signal processor. Thus in array 250A, column 1 represents the response to the first light pulse, column 2 represents the response to the second light pulse, . . . , and column M represents the response to the Mth light pulse.
The response signals in arrays 250A, 260A, 270A, . . . , 290A, 300A may be optionally normalized (blocks 250B, 260B, . . . , 300B) to correct for any variation in light intensity between light pulses. This is accomplished by dividing the values in each column of arrays 250A, 260A, 270A, . . . , 290A, 300A by the corresponding value in row array 240A corresponding to that light pulse. These normalized values are stored in arrays 250N, 260N, 270N, . . . , 290N, 300N. The values in each row of arrays 250A, 260A, 270A, . . . , 290A, 300A (or optionally, the values in each row of arrays of normalized values 250N, 260N, 270N, . . . , 290N, 300N) are then averaged to produce a single column array (250C, 260C, 270C, . . . , 290C, 300C respectively) that represents the respective response from each photodetector 56, 66, 76, . . . , 106 over the time interval sampled. Since the values in each single column array (250C, 260C, 270C, . . . , 290C, 300C respectively) have been averaged over a number of pulses M, luminescence response of the material of the security mark to excitation by stray ambient light is effectively removed. The values at the corresponding row positions of the column arrays 250C, 260C, 270C, . . . , 290C, 300C may then be ratioed (block 250L) to determine the relative response at each band of wavelengths of interest.
Optionally all the values in each array 250C, 260C, 270C, . . . , 290C, 300C may be averaged to produce a single value 250D, 260D, 270D, . . . , 290D, 300D, respectively, that represents the average response over all the samples for each wavelength of interest. These single values may then be ratioed to determine the relative response at each band of wavelengths of interest.
The ratios may be formed in one of several ways. Preferably, as is generally indicated by reference numeral 250L in
In an alternative ratioing method (not shown), a value representing the averaged luminescence intensity at each wavelength range may be divided by a value representing the sum of the averaged luminescence intensities at all of the detected wavelength ranges and then these ratios compared to respective upper and lower limits.
The signal processor assembly 200 is implemented using commercially available logic and digital signal processor integrated circuit units. These integrated circuits are small and inexpensive and have low enough power consumption to implement the required functionality in a hand-held reader that may be battery powered.
An apparatus 10 having an arrangement in accordance with
Thus channel 250 (and the resulting array 250C) represents the response at the 592 nanometer peak, channel 260 (and the resulting array 260C) represents the response at the 610.5 nanometer peak and 270 (and the resulting array 270C) represents the response at the 692 nanometer peak of the emission spectrum.
The ratios of the corresponding values of respective pairs of arrays 250C and 260C, arrays 250C and 270C and arrays 260C and 270C stored in the memory 230M of the signal processor 230 are compared to predetermined ranges of expected ratios for the wavelength bands of interest. In this example the ratio of the 585-595 nanometer wavelength band (i.e., the 592 nanometer peak) to the 605-615 nanometer wavelength band (i.e., the 610.5 nanometer peak) may be compared to the expected ratios for this material. Similarly the ratio of the 585-595 nanometer wavelength band (i.e., the 592 nanometer peak) to the 685-695 nanometer wavelength band (i.e., the 692 nanometer peak) may be compared to the expected ratio for this material. If all the ratios satisfy the criteria of expected ratios the authenticity of the luminescent security mark is confirmed and an indicating device 510 (e.g., a liquid crystal display (LCD), a green indicator light, high frequency tone audible alert, etc.) is activated to indicate the authenticity of the security mark.
If one or more ratios are outside the criteria of expected ratios another indicating device 520 (e.g., an LCD, a red indicator light, low frequency audible alert, etc.) is activated to indicate the lack of authenticity of the security mark. The signal processor also compares overall signal levels stored in memory with criteria for expected signal levels. If the signal level from the monitoring photodetector 32 is too low, this is an indication that the light source 22 is not operating properly and an appropriate indicating device 530 (e.g., an LCD, a flashing red indicator light, audible alert, etc.) is activated. If the signal levels from the photodetector assemblies are too low, this is an indication that the apparatus may not be illuminating the security mark and an appropriate indicating device 540 (e.g., an LCD, a blinking yellow indicator light, beeping audible alert, etc.) is activated.
Important considerations in an apparatus for verifying security marks are the excitation response time of the luminescent material, i.e., the time required for the excitation illumination to produce a useful level of luminescence, and the luminescence lifetime, i.e., the time required for the luminescence intensity to decay to 1/e of its initial intensity (that is, its intensity immediately after the excitation pulse is complete). Additional considerations are the excitation response time and the fluorescence lifetime (i.e., the time required for the fluorescence to decay to its 1/e value) of the fluorescence of the substrate to which the luminescent material is applied. These considerations are especially important if the verification apparatus utilizes a synchronous detection method, which is preferred in the present apparatus for the increased sensitivity it provides.
If the excitation response time and the luminescence lifetime of the luminescent material of the security mark are sufficiently different from the excitation response time and the fluorescence lifetime of the inherent fluorescence of the substrate, these differences can be exploited so that the verification apparatus can effectively ignore the substrate fluorescence.
The excitation response time of the substrate fluorescence is typically significantly less than about ten microseconds and the fluorescence decay time of the substrate fluorescence is typically less than about ten microseconds.
In preferred embodiments of the invention, security mark materials are chosen from among those materials families containing rare earth ions as the luminescent centers. For some of these rare earth ions the luminescent decay times are as much as 30 milliseconds.
For a security mark containing such a rare earth ion on a fluorescing substrate the excitation pulse from the light source 22 might typically be five milliseconds in duration. A 50 microsecond (that is, five times longer than the substrate fluorescence lifetime) delay between the end of the light pulse to the start of sampling of the photodetector signals might be used so that the substrate fluorescence has fully decayed before the sampling begins.
The basic concept of synchronous or lock-in detection in the present apparatus is to take a weak DC luminescence signal from a security mark 12, which is easily contaminated and overwhelmed by ambient noise sources, and convert it to an AC luminescence signal by chopping (pulsing) the excitation source at some frequency. This AC luminescence signal can be detected by a photodiode, the resulting electrical signal band-pass filtered (at the chopping frequency), then amplified and demodulated (i.e., converted back to DC) by a phase sensitive detector that selectively senses a signal only at the chopping frequency. The DC signal is then low-pass filtered and amplified, and this final output is then directly proportional to the light intensity falling on the photodetector. The last low-pass filter is typically chosen to have a frequency bandwidth corresponding to a one second time constant, or 0.125 Hz. This very narrow bandwidth greatly reduces finite-frequency noise at the output of the lock-in amplifier, but passes the desired DC signal. Thus it is possible to detect a signal that is buried in noise by utilizing synchronous detection, and the considerations needed to apply this scheme to luminescent security marks, and expected performance results are described in an example below.
Light emitting diodes having output peaks with wavelengths matching the absorption spectrum of rare earth luminescence materials are available. Typical is a 5 milliwatt (mW) Lumex 380 nanometer LED having a peak emission at 380 nanometers. However, this Lumex LED (and LEDs from other manufacturer's as well) have been found to emit a small amount of visible light V, as shown in the right hand portion of
It should be noted that this reflected light is effectively ignored in the signal processing of the present apparatus because this reflected light will no longer be present when the time-delayed sampling of the photodetectors begins.
The apparatus of the present invention is readily adapted for portable, hand-held use. The housing encloses all of the components of the apparatus, which may be battery powered. The signal processor assembly may be implemented using commercially available low power integrated circuits. The present apparatus may be used as a stand-alone hand-held device or may be operated connected to a data logging system, such as a point-of-sale terminal or a desktop personal computer. The apparatus may be powered by only three AA batteries. Its approximate physical characteristics are: dimensions of less than 8″ in length by less than 4″ in width by less than 2″ in depth; and, a weight is less than 500 grams (with 3 AA batteries). The battery lifetime is estimated to be several hundred hours of continuous use. The apparatus excites a security mark and determines its authenticity in approximately one second. The results of the last several hundred attempts to authenticate a security mark are stored in an on-board memory and may be read out through the USB port on the apparatus.
The optical design of the present apparatus has several advantages over prior art designs for the authentication of luminescent security marks. The present design is a simple retroreflective arrangement that requires minimal optics and is easy to align. A symmetrical arrangement of the photodetector assemblies insures that each of the photodetectors will view the same region of the security mark illuminated. Since each photodetector views the same region of the mark any slight inhomogeneities in the distribution of luminescent material in the security mark will not influence the measured luminescence ratios. A further advantage is achieved by positioning each of the photodetectors at the same distance from the security mark, so that it is not essential that the security mark 12 be exactly at the focal point of lens 30.
If the distance from the collection lens 30 to the security mark 12 is not equal to the focal length of the lens 30, the collected luminescence beam will not be well-collimated and the collected light will not be exactly focused on the active area of each photodetector 56, 66, 76. Positioning each photodetector 56, 66, 76 at an equal distance from the security mark insures an equal degree of focus of the light on each photodetector. This insures that the spatial distribution of light emitted by the security mark arriving at each photodetector 56, 66, and 76 will be the same.
It is also important to focus the luminescence on each detector to a spot size considerably smaller than the detector area to eliminate the possibility of some light missing the detector due to slight misalignments in the optical path.
The folded arrangement of the illumination assembly uses a wavelength-selective beam splitter to direct a substantially collimated excitation beam along an axis toward the security mark. The focusing lens focuses the substantially collimated excitation beam onto the security mark. Light emitted from the security mark travels back along the same axis, is substantially collimated by the focusing lens and passes through the wavelength-selective beam splitter. This folded illumination arrangement reduces the possibility of excitation light from the LED reaching the photodetector assemblies 50, 60, 70, and allows the use of a single lens 30 to both focus the excitation onto the security mark and to collect and substantially collimate the luminescence emitted by the security mark.
The present apparatus requires photodetectors that are quite sensitive to light, and silicon photodiodes are preferred. Silicon photodiodes have several advantages over other photodetectors. First, silicon photodiodes provide reasonably high sensitivity throughout the visible and near-infrared spectral region (400-1100 nanometers), enabling them to detect most of the luminescence wavelengths of interest. Second, silicon photodiodes can be operated with zero voltage bias, i.e., photovoltaic mode, providing the highest sensitivity at the expense of slightly slower response time, which is not a disadvantage for the present application. This permits simplified electronics and facilitates battery-powered operation. Third, silicon photodiodes are available in various sizes (i.e., detector areas), and in the zero bias, or photovoltaic, mode there is no noise penalty for using larger area photodetectors to simplify optical alignment and minimize the possibility of luminescence falling outside the active area of the photodetector. Fourth, silicon photodiodes are both reliable and inexpensive, two very important attributes for commercial apparatus. Silicon photodiodes require a standard transimpedance preamplifier for current to voltage conversion, and the typical circuit for this amplifier is shown in
For increased optical sensitivity silicon avalanche photodiodes or photomultipliers may be employed as the photodetectors, but these types of detectors require higher voltage power supplies that are not as compatible with battery powered portable operation. In fixed applications, where AC power is available, silicon avalanche photodiodes or photomultipliers offer increased responsivity (i.e., a responsivity increase from <1 amp per watt (A/W) for standard silicon photodiodes to ˜50 A/W for silicon avalanche photodiodes). This increased responsivity could significantly decrease the time needed to interrogate each security mark or could permit interrogation at greater distances.
A commercial single-phase lock-in amplifier (EG&G Princeton Applied Research Model 5209) was used to analyze the output signals from the Si photodiode circuitry. The LED was electronically modulated using a Stanford Research DG535 pulse generator. The modulated excitation waveform is square-wave, with an independently variable pulse width and pulse frequency. Since a lock-in amplifier with an electronic band-pass filter centered at the LED modulation frequency is used, only the fundamental cos (ωt) component of the Fourier series expansion of the signal resulting from the square-wave excitation is detected. It should be appreciated that a somewhat larger signal could be obtained by modulating the LED output sinusoidally, so that the entire signal appears at a single modulation frequency. The data shown were collected with a lock-in time constant of one second (selected to meet a criterion of a one second read time), corresponding to a detection bandwidth of 0.125 Hz.
The following Examples 4-9 demonstrate the operation of the present invention. The apparatus arrangement of
A Europium-based commercial phosphor (Kyokko Red LP-RE1 from Kasei Optonix Corp. was mixed with ethyl cellulose (50 weight % phosphor) and β-terpineol by mulling for 5-6 minutes. The resulting paste was screen-printed on standard Avery label stock (No. 8160) using a 325 mesh screen. One coat was applied to each of 5 labels. The films were heated at 110-125° C. for 10 minutes to evaporate any residual solvent.
The printed labels were illuminated for 10 milliseconds by the present apparatus and the luminescence intensities were then measured during a three millisecond window starting about one millisecond later. Intensities were measured through band-pass filters centered at 589 nanometers, 610 nanometers and 694 nanometers for each of the 5 films, the ratios calculated, and the results are given in Table 3. This example demonstrates the ability of the present apparatus to measure a set of characteristic luminescence intensity ratios from a printed security mark.
A Europium-based commercial phosphor (KX-504A from Kasei Optonix Corp. was mixed with ethyl cellulose (50 weight % phosphor) and β-terpineol by mulling for 5-6 minutes. The resulting paste was screen-printed on standard Avery label stock (No. 8160) using a 325 mesh screen. One coat was applied to each of 12 labels. The films were heated at 110-125° C. for 10 minutes to evaporate any residual solvent.
The printed labels were illuminated for 10 milliseconds by the present apparatus and the luminescence intensities were then measured during a three millisecond window starting about one millisecond later. The luminescence intensities were measured through band-pass filters centered at 589 nanometers, 610 nanometers and 694 nanometers for each of the 12 films, the ratios calculated, and the results are given in Table 4. This example demonstrates the ability of the present apparatus to measure a different set of characteristic luminescence intensity ratios from a different printed security mark.
A Europium-based commercial phosphor (KX-504A from Kasei Optonix Corp.) was mixed with ethyl cellulose (50 weight % phosphor) and β-terpineol by mulling for 5-6 minutes. The resulting paste was screen-printed on standard Avery label stock (No. 8160) using a 325 mesh screen. Two coats were applied to each of 10 labels. The films were heated at 110-125° C. for 10 minutes to evaporate any residual solvent.
The printed labels were illuminated for 10 milliseconds by the present apparatus and the luminescence intensities were then measured during a three millisecond window starting about one millisecond later. The luminescence intensities were measured through band-pass filters centered at 589 nanometers, 610 nanometers and 694 nanometers for each of the 10 films, the ratios calculated, and the results are given in Table 5. This example demonstrates that the characteristic luminescence ratios measured by the present apparatus are not affected by the print thickness.
A Europium-based commercial phosphor (KX-504A from Kasei Optonix Corp.) was mixed with ethyl cellulose (50 weight % phosphor) and β-terpineol by mulling for 5-6 minutes. The resulting paste was screen-printed on standard Avery label stock (No. 8160) using a 325 mesh screen. Three coats were applied to each of 11 labels. The films were heated at 110-125° C. for 10 minutes to evaporate any residual solvent.
The printed labels were illuminated for 10 milliseconds by the present apparatus and the luminescence intensities were then measured during a three millisecond window starting about one millisecond later. The luminescence intensities were measured through band-pass filters centered at 589 nanometers, 610 nanometers and 694 nanometers for each of the 11 films, the ratios calculated, and the results are given in Table 6. This example demonstrates that the characteristic luminescence ratios measured by the present apparatus are not affected by the print thickness.
The following two examples show the presence of both substrate fluorescence and security mark luminescence when using continuous excitation and detection. The examples also demonstrate the elimination of the substrate fluorescence by using pulsed excitation and time-delayed luminescence detection.
A Europium-based commercial phosphor (Kasei Optonix Corp. KX-504A) was mixed with ethyl cellulose and a solvent (beta-terpineol) by mulling for 5-6 minutes. The resulting paste was screen-printed on standard Avery label stock (No. 8160) using a 325 mesh screen. Two coats were applied to the label, yielding a coating weight of approximately 4.0 mg phosphor/cm2. The film was heated to 110-125° C. for 10 minutes to evaporate any residual solvent.
Luminescence spectra were then collected using two different methods. In the first method a commercial SPEX® Model Fluorolog®-3 spectrofluorometer, available from HORIBA Jobin Yvon, Inc. of Edison, N.J., was used to collect a luminescence spectrum. The excitation source was a Xe lamp operated in steady-state mode (i.e. excitation constant in time). The excitation wavelength was 394 nanometers and the resulting luminescence was collected with 1 nanometer spectral resolution and 0.1 nanometer step size. The luminescence spectrum is shown in
In the second method a luminescence spectrum was collected using a SPEX® Model Fluorolog®-3 phosphorimeter equipped with a pulsed Xenon light source as the excitation source. The excitation pulse width was 1 microsecond and the pulse repetition rate was 50 Hz. The luminescence was detected 1 msec after the end of the excitation pulse for a time period of 15 msec, i.e. before the arrival time of the subsequent excitation pulse. The excitation wavelength was 394 nanometers and the resulting luminescence was collected with 1 nanometer spectral resolution and 0.5 nanometer step size. The luminescence spectrum is shown in
An Europium-based commercial phosphor (Kasei Optonix Corp. LP-RE1) was mixed with ethyl cellulose and a solvent (beta-terpineol) by mulling for 5-6 minutes. The resulting paste was screen-printed on standard Avery label stock (No. 8160) using a 325 mesh screen. One coat was applied to the label, yielding a coating weight of approximately 2.0 mg phosphor/cm2. The film was heated to 110-125° C. for 10 minutes to evaporate any residual solvent.
Luminescence spectra were then collected using two different methods. In the first method a commercial SPEX® Model Fluorolog®-3 spectrofluorometer was used to collect a luminescence spectrum. The excitation source was a Xe lamp operated in steady-state mode (i.e. excitation constant in time). The excitation wavelength was 394 nanometers and the resulting luminescence was collected with 1 nanometer spectral resolution and 0.1 nanometer step size. The luminescence spectrum is shown in
In the second method a luminescence spectrum was collected using a SPEX® Model Fluorolog®-3 phosphorimeter equipped with a pulsed Xenon light source as the excitation source. The excitation pulse width was 1 microsecond and the pulse repetition rate was 50 Hz. The luminescence was detected 1 msec after the end of the excitation pulse for a time period of 15 msec, i.e. before the arrival time of the subsequent excitation pulse. The excitation wavelength was 394 nanometers and the resulting luminescence was collected with 1 nanometer spectral resolution and 0.5 nanometer step size. The luminescence spectrum is shown in
Examples 10-13 are based upon calculated performance using discrete notch filters (predicted reflectivity and transmission spectra) supplied by Barr Associates, Inc. of Wesfford, Mass. Discrete notch filters having the spectra illustrated in
A commercial phosphor (Kasei Optonix KX-504A) that could be used as a security mark provided luminescence peak intensity ratios that were calculated in the following manner: A luminescence spectrum was first measured using a SPEX® Model Fluorolog®-3 spectrometer. The sample was in the form of a powder loaded in a small (4 mm diameter) quartz tube. The excitation wavelength was 254 nanometers. The emission spectrum was collected with 1 nanometer spectral resolution and 0.1 nanometer step size. Luminescence data were collected from 470-750 nanometers. Calculated reflectivity and transmission spectra for three discrete notch filters were provided by Barr Associates. The peak reflectivities of the notch filters were centered at wavelengths of 589 nanometers, 627 nanometers, and 694 nanometers. The spectral response of these filters is shown in
A commercial phosphor (Kasei Optonix LP-RE1) that could be used as a security mark has luminescence peak intensity ratios that were calculated in the following manner: A luminescence spectrum of the LP-RE1 material was first measured using a SPEX® Model Fluorolog®-3 spectrometer. The sample was in the form of a powder loaded in a small (4 mm diameter) quartz tube. The excitation wavelength was 254 nanometers. The emission spectrum was collected with 1 nanometer spectral resolution and 0.1 nanometer step size. Luminescence data were collected from 470-750 nanometers.
Calculated reflectivity and transmission spectra for three discrete notch filters were provided by Barr Associates. The peak reflectivities of the notch filters were centered at wavelengths of 589 nanometers, 627 nanometers, and 694 nanometers. When used in the apparatus of
Examples 12 and 13 are based upon calculated apparatus performance using Rugate filters whose predicted reflectivity and transmission spectra were supplied by Barr Associates.
A commercial phosphor (Kasei Optonix KX-504) that could be used as a security mark has luminescence peak intensity ratios that were calculated in the following manner: A luminescence spectrum of the KX-504 material was first measured using a SPEX® Model Fluorolog®-3 spectrometer. The sample was in the form of a powder loaded in a small (4 mm diameter) quartz tube. The excitation wavelength was 394 nanometers. The emission spectrum was collected with 1 nanometer spectral resolution and 0.5 nanometer step size. Luminescence data were collected from 425-730 nanometers.
Calculated reflectivity and transmission spectra for three Rugate filters were provided by Barr Associates. The peak reflectivities of the filters were centered at wavelengths of 592 nanometers, 610 nanometers, and 694 nanometers. When used in the apparatus of
A commercial phosphor (Kasei Optonix LP-RE1) that could be used as a security mark has luminescence peak intensity ratios that were calculated in the following manner: A luminescence spectrum of the LP-RE1 material was first measured using a SPEX® Model Fluorolog®-3 spectrometer. The sample was in the form of a powder loaded in a small (4 mm diameter) quartz tube. The excitation wavelength was 394 nanometers. The emission spectrum was collected with 1 nanometer spectral resolution and 0.5 nanometer step size. Luminescence data were collected from 425-730 nanometers. Calculated reflectivity and transmission spectra for three discrete notch filters were provided by Barr Associates.
The peak reflectivities of the notch filters were centered at wavelengths of 592 nanometers, 610 nanometers, and 694 nanometers. When used in the apparatus of
Those skilled in the art, having the benefit of the teachings of the present invention may impart modifications thereto. Such modifications are to be construed as lying within the scope of the present invention, as defined by the appended claims.
This application claims priority to U.S. Provisional Application 60/839,648, filed Aug. 23, 2006.
| Number | Date | Country | |
|---|---|---|---|
| 60839648 | Aug 2006 | US |