FIELD OF THE INVENTION

[0001] The present invention relates to a device, systems and methods for semi- forensically detecting preconfigured patterns, colors and their combination and uses thereof. Specifically, the disclosure relates to a device adapted to selectively excite and detect emission of a preconfigured pattern of photoluminescence sources and their use for authenticating articles of manufacture.

BACKGROUND OF THE INVENTION

[0002] The adulteration, counterfeiting, tampering, unauthorized distribution and sale of various articles of manufacture, such as plastic articles, as well as the authentication issues arising out of 3D printing technologies (as well as printing in general), have emerged as substantial problems for manufacturers, consumers, and governments alike. Likewise, in assigning culpability for misappropriation, the focus has turned to source identifiers.

[0003] Tagging has been requested by manufacturers, distributors and governments alike in order to mitigate the aforementioned issues. Tagging can be done by for example, adding a colorant, a fluorescent compound, or other easily detectable markers.

[0004] However, certain articles of manufacture, for example, food and pharmaceutical packaging are sensitive to toxic tagging technologies, while shelf life and environmental factors such as the exposure to sunlight may adversely affect other tagging technologies by effectively (photo-)bleaching these tagging compounds.

[0005] In addition, tagging technologies for plastics and polymers may cause adverse effects to the properties of the product, or may not be compatible with the production process of the plastic product due to challenging temperatures and pressures encountered in the production process. [0006] Moreover, in certain classes of plastic materials, for example thermoset materials, the taggant materials may interfere with, or be affected by, the mixture of chemicals existing in the mixture.

[0007] It would be therefore highly desirable to provide markers that are compatible with the producing condition of plastic products, and which can be detected using a simple and relatively inexpensive device.

[0008] It is therefore an object of the present invention to provide a marker detecting device, which operates in combination with unique markers that are compatible with the processing conditions of plastic products.

[0009] It is a further process of the invention to provide a device adapted to selectively excite and detect emission of a preconfigured pattern of fluorescent carbon- based materials and their use for authenticating articles of manufacture.

[00010] Other objectives and advantages of the invention will become evident from the following description of embodiments thereof.

[00011] Disclosed, in various embodiments, are devices and systems adapted for detecting a preconfigured color (or spectra) pattern, shape patterns or their combination and uses thereof. Specifically, the disclosure relates to a device adapted to selectively excite and detect hyperspectral emission of a preconfigured pattern of fluorescent carbon-based materials.

[00012] As used herein, the term "fluorescent carbon-based materials" relates to carbon materials having fluorescence properties (for the sake of brevity, the term "fluorescence" would be used herein also to refer interchangeably to photoluminescence (PL)) in the context of this description the "fluorescent carbon-based materials" encompass carbon molecules, carbon-based oligomers and polymer/co-polymer structures, carbon dots (CDs), photoluminescent carbon nanostructures (PCNs) such as graphene quantum dots (fluorescent carbon-based materials), graphene oxide quantum dots, carbon nanotube quantum dots or a combination of one or more of said materials. Specifically, the fluorescent carbon-based materials may originate from any organic carbon source which is non-toxic or otherwise not deleterious to the intended use. The carbon nanotube quantum dots can be single wall nanotube (SWNT), or multi-wall nanotube (MWNT), or a combination thereof.

[00013] In an embodiment, provided herein is a hyperspectral/multispectral imaging system, comprising: an illumination module configured to illuminate a subject; an optical acquisition module adapted to acquire photons emitted from the subject; a display a central processing module (CPM); a display in communication with the CPM; and a memory in communication with the CPM having thereon a processor-readable medium with a set of executable instructions configured to cause the CPM to: in response to activation by a user, illuminate the subject; detect photons emitted from the subject; and display a pattern represented by the emitted photons.

[00014] In another embodiment, provided herein is a method of authenticating an article of manufacture having thereon an area of interest (AOI) adapted to emit photons at a predetermined spectra, in a predetermined pattern, or their combination, comprising: using a hyperspectral/multispectral imaging system, detecting the pattern and/or spectra of photons emitted by the AOI; comparing the detected pattern and/or spectra with a pattern and/or spectra associated with an authentic article of manufacture; and if the pattern and/or spectra detected is homologous to the pattern associated with the authentic article of manufacture, authenticating the article; otherwise providing an indication that the pattern detected is not homologous to the pattern associated with the authentic article of manufacture.

[00015] In yet another embodiment, arranging the plurality of fluorescent carbon- based materials in the area of interest comprises the steps of:

a) providing an ink jet printing system comprising a first print head having at least one aperture, a first inkjet ink reservoir, and a pump configured to supply the first inkjet ink through the aperture;

b) providing a second print head having: at least one aperture, a second inkjet ink reservoir, and a pump configured to supply the second inkjet ink through the aperture; c) providing a conveyor, operably coupled to the first, and the second print heads configured to convey a substrate to each of the first, and second print heads; d) providing and a computer aided manufacturing ("CAM") module, comprising a data processor, a non-volatile memory, and a set of executable instructions stored on the non-volatile memory for receiving a 2D visualization file representing predetermined pattern;

e) generating a file that represents the predetermined pattern for printing;

f) receiving a selection of parameters related to the area of interest, and altering the file representing the predetermined pattern based on at least one of the selection of parameters, wherein the CAM module is configured to control each of the first, and second print heads;

g) providing the first inkjet ink composition, and the second inkjet ink composition; h) using the CAM module, obtaining a generated file representing the 2D pattern; i) using the first print head, forming the pattern corresponding to the first inkjet ink representation in the pattern for printing;

j) curing the pattern corresponding to the first inkjet ink;

k) using the second print head, forming the pattern corresponding to the second inkjet ink representation in the pattern for printing; and

L) curing the pattern corresponding to the second inkjet ink representation.

[00016] In yet another embodiment, the plurality of photoluminescent dots are arranged in a polymer substrate which is a thermoset polymer selected from: poly(epoxide), an acrylic, poly(dimethylsiloxane) thermoset, poly(urethanes), a copolymer thereof or their combination.

[00017] In yet another embodiment, arranging the plurality of photoluminescent dots inside a polymer substrate which is thermoplastic polymer selected from: Acrylonitrile butadiene styrene (ABS), poly(vinylchloride) (PVC), High density poly(ethylene) (HDPE), Low density poly(ethylene) (LDPE), Poly(propylene) (PP), poly(styrene) (PS), poly(methylmethacrylate) (PMMA), Natural rubber (NR), poly(oxymethylene) (POM), Polycarbonate (PC), Poly(ethylene terephthalate) (PET), poly(etheretherketone) (PEEK), poly(caprolactam) (Nylon 6, PA6), a copolymer thereof, terpolymer thereof, or their combination.

[00018] According to some embodiments, the polymeric product is an identification item, and in other embodiments, the polymeric product is an ornamental item.

[00019] In one aspect, the polymeric product is manufactured by the steps of: adsorbing fluorescent carbon-based materials onto a carrier to form a carrier-fluorescent complex; mixing the carrier-fluorescent complex with a thermoset polymer resin, forming a master batch; optionally, diluting the master batch with thermoset polymer resin; and admixing the master batch with the thermoset hardener, thereby initiating curing. According to some embodiments, the master batch is diluted with said thermoset polymer to a concentration of between 0.1-5 %wt. According to some embodiments, the curing comprises crosslinking, photocuring, or a curing combination comprising the foregoing. According to some embodiments, the method comprises a step of molding the process batch prior to curing.

[00020] According to some embodiments, mixing the carrier-fluorescent complex with the thermoset polymer resin is performed at a maximum loading level of between 20-30 %wt of carrier to resin, depending on the carrier and the resin.

[00021] In another aspect, the polymeric product is manufactured by the steps of: adsorbing fluorescent carbon-based materials onto a carrier to form a carrier-fluorescent complex; mixing the carrier-fluorescent complex with a composition comprising a thermoplastic polymer, under extrusion conditions, forming a master batch; and diluting the master batch with a thermoplastic resin, thereby forming a process batch ready for injection molding. According to some embodiments, the extrusion conditions are at between 200°C -300°C and at loading level of 0.1-10 %wt of carrier to resin.

[00022] According to some embodiments, adsorbing fluorescent carbon-based materials onto a carrier comprises the steps of: solubilizing the fluorescent carbon-based materials in a solvent; adding the carrier to the fluorescent carbon-based materials solution under continuous mixing; separating the -fluorescent complex from the solvent; drying the carrier-fluorescent complex; and grinding the carrier-fluorescent complex into a fine powder.

[00023] According to some other embodiments, adsorbing fluorescent carbon- based materials onto a carrier comprises the steps of: solubilizing the carrier in a solvent, optionally, under heating conditions; adding the fluorescent carbon-based materials to the carrier solution and mixing; drying the carrier-fluorescent complex; and grinding the carrier-fluorescent complex into a fine powder. According to some other embodiments, the solubilizing the carrier in a solvent is performed under heating conditions of between 60°C -80°C.

[00024] According to some embodiments, drying the carrier-fluorescent complex is done in a vacuum oven at a temperature of between 60°C -120°C and between 20-50 mBar.

[00025] According to some embodiments, the carrier in the above methods is an organic or inorganic micron sized material examples being - starch, AI203, Ti02, ZnO, Ce02, Si02, CaC03, or a combination thereof. According to some embodiments, the ratio between the fluorescent carbon-based materials and the carrier is between 1:850 and 1:50, or between 100 ppm and 20,000 ppm.

[00026] According to some embodiments, the solvent is selected from: ethanol (EtOH), isopropyl alcohol (IPA), water, or a solvent composition comprising one or more of the foregoing.

[00027] According to some embodiments, the step of mixing the carrier- fluorescent complex is preceded by filtering the carrier-fluorescent complex.

[00028] According to some embodiments, the step of mixing the master batch with the thermoplastic resin is followed by a step of forming the process batch into pellets, rods, powder or a physical form comprising one or more of the foregoing.

[00029] In another aspect, the polymeric product is manufactured by impregnating a thermoplastic polymer with fluorescent carbon-based materials comprising the steps of: forming a powder comprising composite thermoplastic polymer and the fluorescent carbon-based materials; using a first solvent which is thermodynamically compatible with both the thermoplastic polymer and the fluorescent carbon-based materials, solubilizing the powder; and removing the first solvent forming a composite powder of thermoplastic polymer and fluorescent carbon-based materials. According to some embodiments, the method further comprises washing the powder with a second solvent which may optionally be thermodynamically compatible with the fluorescent carbon-based materials only. According to some embodiments, the second solvent is the same as the first solvent. According to some embodiments, the second solvent is acetone.

[00030] According to some embodiments, the step of forming the composite powder of thermoplastic polymer and fluorescent carbon-based materials comprises the following steps: admixing the thermoplastic polymer into a reactor containing the first solvent, forming a polymer solution; while stirring, admixing the fluorescent carbon- based materials into the polymer solution forming composite thermoplastic polymer- fluorescent solution; transferring the composite thermoplastic polymer-fluorescent solution to a dryer; removing the first solvent, forming a coarse cake; and milling the coarse cake, forming a fine powder of composite thermoplastic polymer and fluorescent carbon-based materials. According to some embodiments, the mill is a hammer mill or a ball mill. According to some embodiments of the above methods, the fluorescent carbon- based materials are modified to be thermodynamically compatible with the thermoplastic or thermoset polymer.

[00031] According to some embodiments, the polymeric product manufactured according to the above methods, is an identification item. According to some other embodiments, the polymeric product manufactured according to the above methods, is an ornamental item.

BRIEF DESCRIPTION OF THE FIGURES

In the drawings:

[00032] Fig. 1, schematically illustrates a portable system according to one embodiment of the invention; [00033] Fig. 2, is a schematic illustration of a discrete illumination device, detector and optional filters disposed above the area of interest (AOI); and

[00034] Fig. 3, shows examples of preconfigured patterns of AOI's as detected by (from left to right), detector with increasing spectral resolution, at varying excitation wavelengths.

DETAILED DESCRIPTION OF EMBODIMENTS

[00035] Provided herein are embodiments of systems, devices and methods for detecting a preconfigured hyperspectral pattern and uses thereof. Specifically, the disclosure relates to a device adapted to selectively excite and detect emission of a preconfigured pattern and/or spectra (e.g., color) of fluorescent carbon-based materials and their use for authenticating articles of manufacture.

[00036] The term "and/or" as used herein refers in an embodiment to circumstances where A and/or B can be used as either A alone, B alone or as A and B together. For example, "preconfigured pattern and/or spectra (e.g., color) of carbon pattern indicating compounds" refers to embodiments where the detectors are configured to detect only color of the photoluminescence sources, only the pattern created by the photoluminescence sources, or a combination of color AND pattern of the photoluminescence sources in the area of interest (AOI).

[00037] The articles of manufacture that can be tagged, identified and authenticated using the systems, devices, and methods described herein can be, for example, articles printed using additive manufacturing technologies, oriented circuit boards, food and pharmaceutical packaging, or other articles of manufacture where source identifying is important to ensure consumers, producers, distributors and government of the origin of the items thus tagged.

[00038] Disclosed herein is a system 10, comprising a device 100 with a detector configured to detect photonic emission from a substrate, as schematically illustrated in Fig. 1. The device of Fig. 1 is provided with a detector, a power source and a plurality of excitation sources for emitting electromagnetic radiation (EMR), as further discussed herein below. The device can be configured to be handheld, and in the embodiment shown in the figure, it is powered by a smart phone 200, via cable 150, connected, in this particular example, via USB port 250. Of course, alternatively the device can be connected wirelessly, e.g., via Bluetooth. Device 100 can then recognize a specific substrate, schematically illustrated in the fig. by 300. The plurality of excitation sources for emitting electromagnetic radiation (EMR) in the device and systems described herein, can be adapted to emit EMR with narrow full width at half maximum (FWHM). The electromagnetic radiation source can be a light emitting diode (LED) adapted to provide light at a discrete wavelength, a LASER source (e.g., a laser diode or diodes), or a light source coupled to appropriate optical filter. As indicated, there can be more than one LED thus providing simultaneous excitation at various wavelengths, as there can be more than a single LASER source or light source with optical filters that limit the wavelength spectrum exciting the fluorescent carbon-based materials, for example, carbon polymer dots (CPDs).

[00039] These EMR emitting sources can be, for example, light emitting diodes (LEDs) configured to emit light at a very narrow wavelength without generating heat. In an embodiment, the LEDs can be configured to have a central wavelength (CWL) that coincides with the peak excitation wavelength of fluorescent carbon-based materials forming the pattern or configured to provide a particular color combination (spectra), while the full width at half maximum (FWHM) can be configured to be narrow enough so as not to substantially overlap with the excitation wavelength of other fluorescent carbon-based materials forming the pattern and/or the desired spectra. For example, FWHM of the EMR sources can be between 10 nm and 20 nm., while the FWHM of the photoluminescence sources (PCNs) can be configured to be between 30-40 nm.

[00040] Fig. 2 schematically illustrates the setup of device 100. In the figure, 120 is an actuating button, 130 is an optical future that can be switched between different filters, 110 indicates one or more excitation sources, 300 is the base of device 100, and 350 schematically illustrates samples being analyzed by device 100. [00041] The detector can be used to detect only color emitted from fluorescent carbon sources imbedded homogenously in a polymer or print matrix. Alternatively, the detector can be configured to resolve emitting fluorescent carbon sources features loaded onto an inorganic filler in the size between about 2 pm and about 1000 pm, dispersed heterogeneously in a polymer matrix (in other words, the spatial resolution requirement).

[00042] Notably, by using fluorescent carbon-based materials dispersed in pure form or adsorbed on an inorganic filler, it is possible to achieve the effect of photoluminescence in the AOI completely without any effect on the properties of the matrix. This is made possible because fluorescent carbon-based materials, such as, for example, carbon polymer dots (CPDs), are nanometric or sub-nanometric materials (e.g., between about 0.2 nm and up to 25 nm). Therefore, when embedded in the polymer in pure form, their size is under the light diffraction limit and they are invisible to the naked eye while still fluorescing throughout the bulk of the matrix. Alternatively, and when fluorescent carbon-based materials are adsorbed on inorganic fillers, size reduction techniques can be used to produce fine sub-micron particles that are homogenously dispersed in the matrix and maintain their photoluminescence. The above is unlike inorganic fluorescent pigments which may also be used in such applications, and which will almost always have some effect on the optical properties of the matrix they are blended into. Notably, the size of these pigments cannot be reduced without limit as their photoluminescence depends on their crystal structure which accumulates defects as the size reduces.

[00043] Furthermore, since the fluorescent carbon-based materials used in the compositions, devices and methods provided herein, are stable at high temperatures, high pressure and shear force, show relative inertness to changing chemical environments and are usually more photostable than organic dyes which may perform similarly in terms of initial Quantum Yield (QY), they improve the durability of the marking. This, in combination with their high QY enables their loading into polymeric and ink mixtures in ultra-low levels (e.g., about 10 ppm in various systems, or about lppm in bulk liquids) while retaining significant fluorescence. In an embodiment, "low loading" will depend on the pigmentation of the material tagged/authenticated. Accordingly, a loading of, for example loading of 0.01% (w/w) will be considered low loading in non- or sparsely pigmented items, while 0.1% (w/w) (or between about 100 ppm and about 1000 ppm) may be considered as low loading for pigmented items or systems. This low loading can be advantageous when compared with the loading levels required for other organic or inorganic dyes with requiring loading levels of 0.2% and more up to 5% (w/w).

[00044] Fig. 3 illustrates the different levels of detection that can be achieved by inspecting a tagged item. Looking at the 365 nm range, level 1 detector level 2 detector and level 3 detector provide very different levels of detection. The different Ivels represent different spatial and spectral resolutions. For example, level 2 has a greater spatial resolution than level 1, and level 3 has a greater spectral resolution. Moreover, Fig. 3 only shows two states (A and B), but of course other states can be used, at different wavelength, and a scanning procedure may involve a plurality of such states. The colors in this fig. are identified as follows: 301 - cyan; 302 - dark green; 303 - blue; 304 - orange; 305 - purple; 306 - light green; 307 -turquoise. As can be easily seen in the figure, a variety of identifying patterns can be generated such that when read in a specific sequence using different level detectors, a clear identification of a tagged product can be achieved.

[00045] The term "system" as used herein shall also be taken to include any collection of systems or sub-systems that individually or jointly execute a set, or multiple sets, of instructions to perform one or more functions. Also, the term "system" refers to a logical assembly arrangement of multiple devices, and is not restricted to an arrangement wherein all of the component devices are in the same housing.

[00046] Accordingly and in an embodiment, provided herein is a hyperspectral/multispectral imaging system, comprising: an illumination module configured to illuminate a subject using a plurality of discrete wavelengths in a predetermined sequence; an optical acquisition module adapted to acquire photons emitted from the subject; a display; a central processing module (CPM); a display in communication with the CPM; and a memory in communication with the CPM having thereon a processor-readable medium with a set of executable instructions configured to: in response to activation by a user, illuminate the subject; detect photons emitted from the subject; and display a pattern represented by the emitted photons.

[00047] The system and devices disclosed herein can be adapted to perform hyperspectral and/or multispectral imaging, referring to methods and devices for acquiring hyperspectral and/or multispectral data sets or data-cubes, which typically comprise images where continuously sampled, finely resolved spectral information is provided at each pixel (see e.g., Fig. 3). Additionally, or alternatively, the imaging device 100 of Fig. lmay be a multi-spectral imaging device having a plurality of sensors 120 (as shown in Fig. 2) for collecting spectra (and thus intensity) data in a plurality of different wavelengths, for example 3 to 10 in number (see e.g., Fig. 3), from the predetermined fluorescent carbon-based pattern in the AOI. For example, multi-spectral imaging device 100 may be configured to collect spectra data in 4 or more different wavelengths, or 6 or more different wavelengths.

[00048] The term 'module', as used herein, means, but is not limited to, a software and/or hardware component, such as a Field Programmable Gate-Array (FPGA) or Application-Specific Integrated Circuit (ASIC), which performs certain tasks. A module may advantageously be configured to reside on the addressable storage medium and configured to execute on one or more processors. Thus, a module may include, by way of example, components, such as software components, object-oriented software components, class components and task components, processes, functions, attributes, procedures, subroutines, segments of program code, drivers, firmware, microcode, circuitry, data, databases, data structures, tables, arrays, and variables. The functionality provided for in the components and modules may be combined into fewer components and modules or further separated into additional components and modules.

[00049] In an embodiment, the illumination module used in the devices and systems described herein, implemented in the methods described, can comprise a plurality of electromagnetic radiation emitters configured to emit radiation at a predetermined wavelength range. For example, the plurality (e.g., one EMR emitter per fluorescent carbon-based materials. EMR emitters can be LEDs with discrete central wavelength (CWL), for example, as illustrated in Fig. 3, between about 365 nm and about 425 nm (purple); between about 435 nm and about 480 nm (cyan); between about 365 nm and about 425 nm (purple); between about 495 nm and about 540 nm (green); and between about 600 nm and about 615 nm (purple), with FWHM in each of about 10 nm.

[00050] Furthermore, the plurality of EMR emitters can be configured to illuminate the sample discretely (in other words, one at a time), in a preconfigured sequence. For example, illumination of a first AOI can have the sequence Green:Cyan:Orange; while illumination of a second AOI can have the sequence Purple:Cyan:Green. The response in each illumination sequence can then be recorded and form a part of the authentication procedure.

[00051] Further, wherein the optical acquisition module comprises a detection element that is a photodetector, a charge-coupled device (CCD), diode array, complimentary metal-oxide sensor device (CMOS), a focal plane array or a detection element comprising one or more of the foregoing. The optical acquisition module is configured generally to parse received image into multiple distinct classes based on which axes of the data-cube (portion or all the AOI) are sampled at a given instant. For example, using dispersive approaches to hyperspectral imaging, the optical acquisition module can instantaneously sample the pattern along the spectral axis (e.g., from about 190 nm to about 720 nm) and along one spatial axis (see e.g., top row, Fig. 3 level 2 detector), but the other spatial axis must be scanned in time to build up a full data-cube. In an embodiment, light that impinges on an entrance slit can be dispersed through a grating or a prism, and the dispersed light is imaged onto a two-dimensional detector array. By scanning the slit relative to the scene in a reciprocating (in other words, back-and-forth) manner, the full datacube is built up and displayed using the device/system display (see e.g., 200, Fig. 1).

[00052] Other methods can be used in other embodiments to provide the necessary quantitative measurements for detecting and authenticating the pattern and/or spectra (color) of fluorescent carbon-based materials described. For example, Infrared (IR) spectroscopy that is based on the interaction with chemical substances of infrared irradiation having a wavelength between 0.77 pm and 1000 pm. A segment of IR spectroscopy, referred to as near infrared (NIR) spectroscopies, uses radiation wavelengths between about 0.77 pm and about 2.5 pm. IR and NIR spectroscopies generally involves the absorption of radiation as it passes through a sample. The absorption frequencies can therefore provide information regarding the chemical and physical characteristics or the molecular structure of the irradiated substance and its composition.

[00053] Moreover, the CPM is in electronic communication with a library comprising the hyperspectral and/or multispectral patterns. The library can serve as reference for the pattern detected and can include expected emission spectra at each wavelength as a function of the spatial resolution used in the AOI. Accordingly, the set of executable instructions are further configured to cause the CPM to analyze the detected pattern, and to provide a comparison between the detected pattern and the pattern obtained from the library. The comparison can then be used to authenticate the article of manufacture as identical to the source, or as a fake if the degree of homology (in other words, identity) is below a certain threshold, for example, less than 95%, or less than 90%, or in circumstances where the article has been subjected to intensive wear and tear, even less.

[00054] The subject of the analysis is a substrate forming a portion of the article of manufacture, which can either be exposed to the environment, or otherwise concealed. Accordingly, the subject can be a substrate comprising an area of interest (AOI) adapted to emit photons at a predetermined spectrum in a predetermined pattern, wherein the predetermined pattern is the pattern displayed. As illustrated in Fig. 3, the pattern can comprise a plurality of fluorescent carbon-based materials arranged in an embodiment as an array of unique combination (that can be stored in the library). As illustrated, the area of interest can be comprised of a plurality of fluorescent carbon-based materials arranged in a two-dimensional formation adapted to produce the predetermined pattern. That pattern is then recognized by the device and compared with the pattern stored in the linked library, whereupon either the final authentication determination is provided, or the detected pattern and the stored pattern are compared by either overlaying or by rendering the patterns on the display - side-by-side. As indicated hereinabove, the pattern can have dimensions that are less than half the wavelength of visible light, thus making the pattern invisible to the naked eye.

[00055] The output of the detection device can vary from providing the average value of chroma (the strength of the surface color), hue (the dominant wavelength mode) and lightness of the whole sample (AOI), as well as degree of saturation when discretely illuminated at each wavelength provided by the plurality of EMR emitters. These values can then be compared with stored values of an authentic sample and be used to verify the source of the sample. Also, the detecting device can be configured to recognize 2D spatial arrangements of patterns and compare those with stored patterns. Moreover, when hyperspectral imaging is used in the detection, the actual emission spectral bands can be used.

[00056] Embodiments described herein may comprise or utilize a special purpose or general-purpose computer including computer hardware, such as, for example, one or more processors (e.g., central processing module, CPM) and system memory, as discussed in greater detail below. Embodiments described herein also include physical and other computer-readable media for carrying or storing computer-executable instructions and/or data structures. Such computer-readable media can be any available media that can be accessed by a general purpose or special purpose computer system. Computer-readable media that store computer-executable instructions are physical storage media. Computer-readable media that carry computer-executable instructions are transmission media. Thus, by way of example, and not limitation, embodiments of the invention can comprise at least two distinctly different kinds of computer-readable media: computer storage media and transmission media.

[00057] Forming the pattern can be done in an embodiment, using inkjet printing, as indicated, by creating minimally loaded inkjet inks having the fluorescent carbon-based materials dispersed therein, capable of emitting photons in response to excitation at discrete wavelengths.

[00058] In an embodiment, arranging the plurality of fluorescent carbon-based materials in the two-dimensional formation thus forming the predetermined pattern detected by the devices and systems provided can comprises: providing an inkjet printing system comprising: a first print head having: at least one aperture, a firs inkjet ink reservoir, and a pump configured to supply the first inkjet ink through the aperture; a second print head having: at least one aperture, a second inkjet ink reservoir, and a pump configured to supply the second inkjet ink through the aperture; a conveyor, operably coupled to the first, and the second print heads configured to convey a substrate to each of the first, and second print heads; and a computer aided manufacturing ("CAM") module, comprising: a data processor; a non-volatile memory; and a set of executable instructions stored on the non-volatile memory for: receiving a 2D visualization file representing predetermined pattern; generating a file that represents the predetermined pattern for printing; receiving a selection of parameters related to the area of interest; and altering the file representing the predetermined pattern based on at least one of the selection of parameters, wherein the CAM module is configured to control each of the first, and second print heads; providing the first inkjet ink composition, and the second inkjet ink composition; using the CAM module, obtaining a generated file representing the 2D pattern; using the first print head, forming the pattern corresponding to the first inkjet ink representation in the pattern for printing; curing the pattern corresponding to the first inkjet ink; using the second print head, forming the pattern corresponding to the second inkjet ink representation in the pattern for printing; and curing the pattern corresponding to the second inkjet ink representation.

[00059] In some embodiments, the fluorescent carbon-based materials can be nano-sized (of less than 10 nm in size) structures of carbon molecules (more than a single atom) having dimensionality that is anywhere from quasi-one dimension (e.g., quantum dot, nanoribbon, nanobelt), to three dimensional (e.g., multilayer graphene structures). Encompassed in these nano-sized structures, are graphene, graphdiyne, fullerene, nanocage, multilayer graphene dot, nanodiamond, nanotube, nanowire, nanohorn, or a carbon dots composition comprising one or more of the foregoing.

[00060] In some embodiments, the polymeric products are characterized as having uniform fluorescence. While in other embodiments, the polymeric products have a patterned fluorescence. The polymeric products may also comprise fluorescent carbon- based materials having different emission wavelengths producing different colors under electromagnetic radiation (EMR). Polymeric products having unique patterning can be used in authentication and tagging of products. Thus, in some embodiments, the polymeric product is an identification item.

[00061] Other applications of the polymeric product of the invention may have a more aesthetic or decorative value. Thus, in some embodiments, the polymeric product is an ornamental item.

[00062] Detecting, which in another embodiment also includes quantifying emission spectra, can be done, by detecting luminescence of the measured pattern. Luminescence spectroscopy involves the measurement of photon emission from molecules. It can include photoluminescence such as fluorescence and phosphorescence, which are emissions from a substance resulting from its excitation by radiation absorption, as well as chemiluminescence, where the emission is induced by a chemical reaction. The emitted radiation is characteristic of the molecular structure, size and composition. Accordingly, manipulating the structure, size and composition of both the fluorescent carbon-based materials (interchangeable with CQDs), as well as the inkjet ink composition, it is possible to fabricate an AOI having a detectable, repeatable pattern.

[00063] For example, by using a photodetector array (e.g., a PIN diode array) with different color filters and EMR sources based on the plurality of CQDs used in the pattern, as well as provide an UV/VIS/NIR bandpass(es) color filter(s) operably coupled to a photodetector array. Alternatively, a (scanning) diffraction grating (in the case of hyperspectral imaging) coupled to a photodetector array can be used to determine the spectrum profile emitted from the plurality of CQDs. Detection can be quantified, yielding peak emission, half peak baseline, intensity and area under the curve (AUC), as well as ratios of the foregoing, as a function of excitation wavelength (see e.g., Fig 3); all which can be added to the linked library database at the device or system and used to compare with the test sample obtained by an end user or intermediate downstream (pipeline or supply chain).

[00064] As a point of clarification, the control over peak emission spectra of the photoluminescence sources is not necessarily solely a function of size, but of other factors as well, for example; the type of photoluminescence sources (e.g., fluorescent carbon- based materials, lanthanide nanorod, or MWCNT) the extent and location of surface defects in the fluorescent carbon-based materials when used, type and degree of substitution of various functional groups (e.g., carboxylate) as well as uniformity of size distribution and other factors. Accordingly, it is contemplated that fluorescent carbon- based materials having exactly the same overall average D3,2 particle size (e.g., ~5.0 nm), would nevertheless have peak emission spectra that is shifted between about 20 nm and about 80 nm.

[00065] One, all or some of electromagnetic radiation (EMR) sources can be incorporated in a handheld device housing having: a display; a processing module comprising a processor in communication with a linked library containing original pattern emission spectra at a specific wavelength, of the carbon quantum dot formed on the pattern in the AOI on the article of manufacture sought to be identified and/or authenticated; the processor further being in communication with: the plurality of electromagnetic radiation sources; a detector (e.g., a photodetector) configured to detect fluorescence, phosphorescence, chemiluminescence or their combination (and can further comprise additional optical color filters); the display; and a non-volatile memory having thereon a processor-readable medium with a set of executable instructions configured to: receive a reading from the detector; retrieve from the linked library a predetermined: emission spectra; and if the detected pattern emission spectra at a specific wavelength, retrieved from the detector correlates with the pattern emission spectra, at the predetermined specific wavelength, wavelength range or wavelength range segments that were retrieved from the linked library, authenticating the article of manufacture using the display; else identifying the article as non-authentic.

[00066] In an embodiment, the devices and systems described herein are being used in the methods disclosed. Accordingly, provided herein is a method of authenticating an article of manufacture having thereon an area of interest (AOI) adapted to emit photons at a predetermined spectra, in a predetermined pattern and/or spectra, comprising: using a hyperspectral/multispectral imaging system, detecting the pattern and/or spectra (color) of photons emitted by the photons in response to exposure to a plurality of discrete EMR sourced emitting discrete wavelength at a predetermined sequence (wherein the discrete wavelength is between about 200 and 500 nm); comparing the detected pattern and/or spectra with a pattern associated with an authentic article of manufacture; and if the pattern and/or spectra detected is homologous to the pattern and/or spectra associated with the authentic article of manufacture, authenticating the article; otherwise providing an indication that the pattern and/or spectra detected are not homologous to the pattern associated with the authentic article of manufacture. In other words, comparing observed pattern and/or spectra vs. stored, data, whether remotely or locally.

[00067] As indicated, the methods using the PCNs' patterns disclosed and claimed herein, implemented using the devices and systems described herein can further comprise comparing the detected emission pattern and/or spectra to a predetermined pattern and/or spectra corresponding to an authentic identity; and if the detected spectra correlates with the predetermined emission pattern and/or spectra, authenticating the article; else identifying the article as non-authentic. The term "authentic" as used herein means that the pattern and/or spectra detected by the device has high correlation with the emission pattern and/or spectra obtained at the original source.

[00068] To clarify, in the description that follows, embodiments are described with reference to acts that are performed by one or more computing systems. These computing systems can be co-located or remote from each other and connected through various types of networks. The computing systems can be, for example, the handheld device disclosed, a backend management server with the pattern database library, and the like. If the computing systems are distributed (in other words not co-located or otherwise hardwired), the housing comprising the plurality of EMR sources (configured to emit EMR at discrete wavelength range of between NMT about 500 nm, or below full visible wavelength range), can further comprise a transceiver configured to initiate communication with remote computing systems. In other words, the EMR source is an actinic radiation source, configured to produce photochemical reaction in the pattern disposed on the substrate. So, for example, each EMR source can be configured to emit electromagnetic radiation at a wavelength between about 0.8 nm (laser equipped with power stabilizer) and about 450 nm, or between about 160 nm and about 300 nm, for example, between 190 nm and 250 nm.

[00069] If such steps are implemented in software, one or more processors of the associated computing system(s) (e.g., CPM) that performs the act direct the operation of the computing system in response to having executed computer-executable instructions. An example of such an operation involves the manipulation of data. The computer- executable instructions (and the manipulated data) may be stored in the memory of the computing system. Computing system may also contain communication channels that allow the computing system to communicate with other processors and sensors over, for example, service bus.

[00070] Embodiments described herein may comprise or utilize a special purpose or general-purpose computer including computer hardware, such as, for example, one or more processors (e.g., central processing module, CPM) and system memory, as discussed in greater detail below. Embodiments described herein also include physical and other computer-readable media for carrying or storing computer-executable instructions and/or data structures. Such computer-readable media can be any available media that can be accessed by a general purpose or special purpose computer system. Computer-readable media that store computer-executable instructions are physical storage media. Computer-readable media that carry computer-executable instructions are transmission media. Thus, by way of example, and not limitation, embodiments of the invention can comprise at least two distinctly different kinds of computer-readable media: computer storage media and transmission media.

[00071] Computer storage media includes RAM, ROM, EEPROM, CD-ROM or other optical disk storage, magnetic disk storage or other magnetic storage devices, or any other medium which can be used to store desired program code means in the form of computer-executable instructions or data structures and which can be accessed by a general purpose or special purpose computer.

[00072] The term "module" is used herein to refer to software computer program code and/or any hardware or circuitry utilized to provide the functionality attributed to the module. Further, the term "module" or "component" can also refer to software objects or routines that execute on the computing system. The different components, modules, engines, and services described herein may be implemented as objects or processes that execute on the computing system (e.g., as separate threads).

[00073] Further, the CPM may be operably coupled to the various modules and components with appropriate circuitry may also be used herein, the term(s) "operably coupled to", "coupled to", and/or "coupling" includes direct coupling between items and/or indirect coupling between items via an intervening item (e.g., an item includes, but is not limited to, a component, an element, a circuit, an engine, and/or a module) where, for indirect coupling, the intervening item does not modify the information of a signal but may adjust its current level, voltage level, and/or power level. As may further be used herein, inferred coupling (i.e., where one element is coupled to another element by inference) includes direct and indirect coupling between two items in the same manner as "coupled to". As may even further be used herein, the term "operable to" or "operably coupled to" indicates that an item includes one or more of power connections, input(s), output(s), etc., to perform, when activated, one or more its corresponding functions and may further include inferred coupling to one or more other items. As may still further be used herein, the term "associated with", includes direct and/or indirect coupling of separate items and/or one item being embedded within another item. [00074] As may also be used herein, the terms "central processing module", "module", "processing circuit", and/or "processing unit" may be a single processing device or a plurality of processing devices. Such a processing device may be a microprocessor, micro-controller, digital signal processor, microcomputer, central processing unit, field programmable gate array, programmable logic device, state machine, logic circuitry, analog circuitry, digital circuitry, and/or any device that manipulates signals (analog and/or digital) based on hard coding of the circuitry and/or operational instructions. The processing module, processing circuit, and/or processing unit may have an associated memory and/or an integrated memory element, which may be a single memory device, a plurality of memory devices, and/or embedded circuitry of the processing module, module, processing circuit, and/or processing unit. Such a memory device may be a read-only memory, random access memory, volatile memory, non-volatile memory, static memory, dynamic memory, flash memory, cache memory, and/or any device that stores digital information. Note that if the processing module, module, processing circuit, and/or processing unit includes more than one processing device, the processing devices may be centrally located (e.g., directly coupled together via a wired and/or wireless bus structure) or may be distributed (e.g., cloud computing via indirect coupling via a local area network and/or a wide area network). Further note that if the processing module, module, processing circuit, and/or processing unit implements one or more of its functions via a state machine, analog circuitry, digital circuitry, and/or logic circuitry, the memory and/or memory element storing the corresponding operational instructions may be embedded within, or external to, the circuitry comprising the state machine, analog circuitry, digital circuitry, and/or logic circuitry. Still further note that, the memory element may store, and the processing module, module, processing circuit, and/or processing unit executes, hard coded and/or operational instructions corresponding to at least some of the steps and/or functions illustrated in one or more of the figures. Such a memory device or memory element can be included in an article of manufacture. [00075] The terms "a", "an" and "the" herein do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The suffix "(s)" as used herein is intended to include both the singular and the plural of the term that it modifies, thereby including one or more of that term (e.g., the network(s) includes one or more network). Reference throughout the specification to "one embodiment", "another embodiment", "an embodiment", and so forth, means that a particular element (e.g., feature, structure, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.

[00076] The term "system" shall also be taken to include any collection of systems or sub-systems that individually or jointly execute a set, or multiple sets, of instructions to perform one or more functions. Also, the term "system" refers to a logical assembly arrangement of multiple devices, and is not restricted to an arrangement wherein all of the component devices are in the same housing.

Examples

[00077] The following are examples of use that illustrate some of the many uses made possible by the flexible methods and device of the invention.

Example 1

[00078] Using a multispectral device to Resolve and authenticate a plastic part made of the polymer Acrylonitrile butadiene styrene (ABS) by examining the color generated by the emission of CPDs adsorbed onto micron or sub-micron sized silica particles or CaC0 ₃ powder which are dispersed in a thermoplastic material in a homogenous way. The sample is excited with light in different wavelengths (365nm, 395nm, 420nm) and the emission and color response, resulting from the combination of the fluorescent carbon materials with the polymer and possibly a pigment, yields a different value in the color space for each wavelength. The resulting values are compared with a pre-stored reference sample to determine the authenticity of the article.

Example 2

[00079] Using a multispectral device to Resolve and authenticate a plastic part made of the polymer Acrylonitrile butadiene styrene (ABS) by examining the color generated by the emission of CPDs dispersed directly in a thermoplastic material in a homogenous way following extrusion and molding. The sample is excited with light in different wavelengths (365nm, 395nm, 420nm) and the emission and color response, resulting from the combination of the fluorescent carbon materials with the polymer and possibly a pigment, yields a different value in the color space for each wavelength. The resulting values are compared with a pre-stored reference sample to determine the authenticity of the article.

Example 3

[00080] Using a multispectral device to resolve and authenticate a plastic part made of the polymer Acrylonitrile butadiene styrene (ABS) by examining the color generated by the emission of CPDs adsorbed onto micron or sub-micron sized silica particles or CaC03 powder which are dispersed in a thermoplastic material in a heterogenous way. The sample is excited with light in different wavelengths (365nm, 395nm, 420nm) and the emission and color response, resulting from the combination of the fluorescent carbon materials with the polymer and possibly a pigment, yields a different value in the color space for each wavelength. The resulting values are compared with a pre-stored reference sample to determine the authenticity of the article. In addition, the emitting micron sized carriers can be also spatially resolved and analyzed for their proportion in the total population as well as for their size and other shape parameters (such as curvature, X/Y/Z proportion etc.) Example 4

[00081] Using a Hyperspectral device to resolve and authenticate a plastic part made of the polymer Acrylonitrile butadiene styrene (ABS) by examining the color generated by the emission of CPDs adsorbed onto micron or sub-micron sized silica particles or CaC03 powder which are dispersed in a thermoplastic material in a heterogenous way. The sample is excited with light in different wavelengths (365nm, 395nm, 420nm) and the emission and color response, resulting from the combination of the fluorescent carbon materials with the polymer and possibly a pigment, yields a different spectral emission pattern for each of the different fluorescent carbon materials present in the sample. The resulting parameters are then compared with a pre-stored reference sample to determine the authenticity of the article:

[00082] The emitting micron sized carriers are spatially resolved and analyzed for their proportion in the total population as well as for their size and other shape parameters (such as curvature, X/Y/Z proportion etc.)

[00083] The spectral line shape emitted from each particle (Since multiple illumination sources are used, then the resulting spectral line shape is different for each of these illumination sources).

[00084] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Embodiments of the invention have been described by way of illustration, it being understood that the invention may be carried out with many variations, modifications, and adaptations. Accordingly, the appended claims as filed and as they may be amended, are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.