Patent Grant
10532596
This application claims priorities under 35 U.S.C. § 119 to Korean Patent Application Nos. 10-2017-0093746 and 10-2017-0103997 filed on Jul. 24, 2017 and Aug. 17, 2017, respectively, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety.
The present disclosure relates to a structure for preventing counterfeit, falsification or reuse, its manufacturing method and a method for discriminating counterfeit, falsification or reuse using the same, and more particularly, to a structure for preventing counterfeit, falsification or reuse by means of an up-converting material and gap plasmon polariton in the gap, its manufacturing method and a method for discriminating counterfeit, falsification or reuse using the same.
Currently, counterfeits increasingly sell across all business day by day. To prevent counterfeiting and reuse of counterfeits, various technologies to prevent counterfeit and falsification using braille, hologram or special inks have been developed.
However, these technologies still do not eradicate counterfeits because counterfeit or falsification is committed through counterfeit experts, and counterfeit or falsification is difficult for users to discriminate. Moreover, the reuse of products such as packaging boxes and containers to which braille or hologram is attached poses a problem, making it more difficult to eradicate counterfeits.
In this circumstance, there is an earlier report of an anti-counterfeit structure using a plasmonic amplification phenomenon induced by metal nanowire and metal film with an up-conversion (UC) material that absorbs infrared light and emits visible light interposed between (Adv. Funct. Meter. 2016, 26,7836). However, this structure has a structural method for preventing the reuse, but to this end, it needs to use extra pollutants, and because there is no special encoding, attempts to reproduce may be made.
Therefore, in view of these many problems, there is a demand for the development of low-cost, easy-to-manufacture anti-counterfeit technology to prevent the reuse by discouraging attempts to reproduce through pattern encoding, and easily discriminate counterfeit.
The present disclosure is designed to solve the aforesaid problems, and therefore, the present disclosure is directed to providing a structure for preventing counterfeit, falsification or reuse that allows a pattern indicating a genuine product to be easily identified with an eye through infrared light irradiation.
The present disclosure is further directed to providing a structure for preventing counterfeit, falsification or reuse that is fundamentally impossible to re-assemble after deformation of the structure in order to prevent counterfeit, falsification or reuse.
According to an aspect of the present disclosure, there is provided a structure for preventing counterfeit, falsification or reuse, including a metal layer, a photoconversion pattern layer including a plurality of photoconverting nanoparticles formed on the metal layer, a metal pattern layer placed on the metal layer and the photoconversion pattern layer, and an adhesive film placed on the metal pattern layer.
The metal pattern layer may be formed by islanded metal nanoparticles.
A gap plasmon polariton phenomenon may take place between the metal layer and the metal pattern layer.
The photoconversion pattern layer may form a second encoding pattern, the metal pattern layer may form a first encoding pattern, and a visible pattern area at which a photoconversion amplification phenomenon takes place when infrared light is applied may be formed at an overlapping part between the first encoding pattern and the second encoding pattern.
Each of the metal layer and the metal pattern layer may be independently any one selected from gold (Au), silver (Ag), copper (Cu), aluminum (Al), titanium (Ti), chromium (Cr), indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), and fluorine-doped tin oxide (FTO).
The photoconverting nanoparticles may have an average diameter of 5 to 300 nm.
The photoconverting nanoparticles may be any one selected from the group consisting of halide, chalcogenide and metal oxide doped with ytterbium (Yb), erbium (Er), thulium (Tm), yttrium (Y) or mixtures thereof.
The adhesive film may be separated from the metal pattern layer by an external force or heat.
According to another aspect of the present disclosure, there is provided a method for manufacturing a structure for preventing counterfeit, falsification or reuse, including (a) forming a metal pattern on a substrate, (b) transferring the metal pattern to an adhesive film to manufacture the adhesive film having a metal pattern layer, (c) preparing a metal substrate, (d) forming a photoconversion pattern including photoconverting nanoparticles on the metal substrate to manufacture the substrate having a photoconversion pattern layer, and (e) placing the adhesive film having the metal pattern layer on the substrate having the photoconversion pattern layer to form a visible pattern area which is an overlapping part between the photoconversion pattern layer and the metal pattern layer.
The adhesive film at the step (b) may be an adhesive tape or a thermal release tape.
A gap plasmon polariton phenomenon may take place between the metal substrate and the metal pattern.
A photoconversion amplification phenomenon may take place at the visible pattern area at the step (e) when infrared light is applied.
The substrate at the step (a) may be a substrate having a layer of any one selected from graphene, transition metal dichalcogenide (TMDC) materials, graphite, SiC, SiNx, AlN, and diamond.
The metal pattern at the step (a) may be formed by any one method selected from photo lithography, electron beam lithography, X-ray lithography, ion beam lithography, and soft lithography.
The metal pattern at the step (a) may form a separate align key at a preset location so that a pattern matching to the align key may be transferred to the adhesive film together at the step (b).
The metal substrate at the step (c) may have imprint matching to the align key formed in the adhesive film.
The photoconversion pattern at the step (d) may be formed by patterning with the alignment to the imprint matching to the align key such that an overlapping part between the photoconversion pattern and the metal pattern may be formed.
After the adhesive film metal pattern and the photoconversion pattern on metal film are overlapped with the alignment to the imprint matching to the align key at the step (e), removing a transferred part of the pattern matching to the align key of the adhesive film may be additionally performed.
The photoconversion pattern may be formed by any one method selected from photo lithography, electron beam lithography, X-ray lithography, ion beam lithography, and soft lithography.
The metal pattern at the step (a) may be formed with a thickness of 2 to 15 nm.
After the step (a), a dewetting process involving heating at 200 to 1000° C. may be performed so that the metal pattern may be formed by islanded metal nanparticles.
After the step (b), removing graphene transferred to the adhesive film having the metal pattern layer may be additionally performed.
According to still another aspect of the present disclosure, there is provided a packaging box or container for preventing counterfeit, falsification or reuse including the structure.
The structure may be mounted on the surface or an opening of the packaging box or container.
According to further another aspect of the present disclosure, there is provided a method for discriminating counterfeit, falsification or reuse, including 1) applying infrared light to the structure, and (2) identifying counterfeit, falsification or reuse of the structure by identifying a light emission pattern appearing on the structure to which the infrared light is applied.
The step (2) may include identifying the light emission pattern with an eye or using a visible light detection device.
The structure for preventing counterfeit, falsification or reuse according to the present disclosure allows a pattern indicating a genuine product to be easily identified with an eye through infrared light irradiation.
Furthermore, the structure for preventing counterfeit, falsification or reuse according to the present disclosure is fundamentally impossible to re-assemble after deformation of the structure caused by disassembly of a packaging container, thereby preventing counterfeit, falsification or reuse.
Hereinafter, many aspects and various embodiments of the present disclosure are described in further detail.
Hereinafter, the embodiments of the present disclosure are described in sufficient detail with reference to the accompanying drawings to enable those having ordinary skill in the technical field pertaining to the present disclosure to easily practice the present disclosure.
However, the following description is not intended to limit the present disclosure to particular embodiments, and in describing the present disclosure, when a detailed description of related known technology is deemed to render the essence of the present disclosure ambiguous, its detailed description is omitted herein.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the term “comprises” or “comprising”, when used in this specification, specify the presence of stated features, integers, steps, operations, elements, components, or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or groups thereof.
The metal layer may be of a 2-dimensional (2D) metal thin film type, and is preferably at least one metal selected from noble metal materials having low absorption loss in the metal itself, such as gold (Au), silver (Ag) and copper (Cu), or alloy containing at least one metal as a main component, but the scope of the present disclosure is not limited thereto, and all possible materials that can excite plasmons, including aluminum (Al), titanium (Ti), chromium (Cr), indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), and fluorine-doped tin oxide (FTO), can be applied.
The thickness of the metal layer may be preferably 10 nm or more, and more preferably 100 nm or more, to obtain a sufficient gap plasmon polariton effect while blocking visible light penetration.
The photoconversion pattern layer may be formed by a plurality of photoconverting nanoparticles formed on the metal layer.
The photoconverting nanoparticles may be any one selected from the group consisting of halide, chalcogenide and metal oxide doped with ytterbium (Yb), erbium (Er), thulium (Tm), yttrium (Y) or their mixtures, but the scope of the present disclosure is not limited thereto, and all nanoparticles by which photoconversion can take place are available.
An average diameter of the photoconverting nanoparticles is closely related to a gap distance between the metal layer and the metal pattern layer, and the gap distance required to have a gap plasmon polariton effect may be appropriately selected based on the metal type of the metal layer and the metal pattern layer, and may be preferably 5 to 300 nm, and in case that the average diameter is beyond the lower limit and the upper limit, a gap plasmon polariton effect may not appear. Accordingly, the average diameter of the photoconverting nanoparticles is preferably 5 to 300 nm.
For example, in case that the metal layer and the metal pattern layer is made of silver (Ag), the average diameter of the photoconverting nanoparticles is preferably 5 to 300 nm. When the average diameter of the photoconverting nanoparticles is less than 5 nm, a gap plasmon polariton effect does not appear, and when the average diameter is greater than 300 nm, the gap distance between the metal layer and the metal pattern layer increases and a gap plasmon polariton effect does not appear, and thus, visible light may not be produced even upon irradiation with infrared light. That is to say, in case that the average diameter of the photoconverting nanoparticles is less than 5 nm or greater than 300 nm, for infrared light of 780-2000 nm wavelengths, the gap distance is outside of an effective gap distance for producing a gap plasmon polariton effect.
Accordingly, the thickness of the photoconversion pattern layer may be adjusted based on the average diameter of the coated photoconverting nanoparticles.
The metal pattern layer is placed on the metal layer and the photoconversion pattern layer. Accordingly, an overlapping part is formed in which the photoconversion pattern layer and the metal pattern layer overlap with each other, and this part may form a visible pattern area due to a gap plasmon polariton effect.
The metal pattern layer may be formed by islanded metal nanoparticles in a dewetting process.
The adhesive film may be placed on the metal pattern layer.
The adhesive film can easily separate from the metal pattern layer by an external force or heat, and may be an adhesive tape or a thermal release tape. The adhesive film may cap the structure per se, and after detached, the adhesive film may form a separate capping structure.
The metal pattern layer is preferably at least one metal selected from noble metal materials having low absorption loss in the metal itself, such as gold (Au), silver (Ag) and copper (Cu), or alloy containing at least one metal as a main component, but the scope of the present disclosure is not limited thereto, and all possible materials that can excite plasmons, including aluminum (Al), titanium (Ti), chromium (Cr), indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), and fluorine-doped tin oxide (FTO), can be applied.
Accordingly, in the structure for preventing counterfeit, falsification or reuse according to the present disclosure, the metal pattern layer may form a first encoding pattern (corresponding to pattern A), the photoconversion pattern layer may form a second encoding pattern (corresponding to pattern B), and a visible pattern area may be formed at the overlapping part at which the first encoding pattern and the second encoding pattern are aligned on micro or nano level, where a photoconversion amplification phenomenon takes place when infrared light is applied.
First, a metal pattern is formed on a substrate (Step a).
The substrate is preferably a substrate having a graphene layer, and the metal pattern (corresponding to pattern A) is preferably formed on the graphene layer. However, the scope of the present disclosure is not limited to the graphene layer, and all materials that can form a layer of 100 nm or less in thickness on the substrate, including 2D materials such as transition metal dichalcogenide (TMDC) materials, graphite, SiC, SiNx, AlN, and diamond, may be applied.
The metal pattern may be formed by a method such as photo lithography, electron beam lithography, X-ray lithography, ion beam lithography and soft lithography, but the scope of the present disclosure is not limited thereto.
The metal pattern may be formed by depositing a metal thin film with the thickness of 2 to 15 nm, and performing a dewetting process involving heating at the temperature of 200 to 1000° C. to form islanded metal nanoparticles.
The deposition of metal nanoparticles may be performed by a method such as spin coating, spray coating, dipping coating, and drop coating.
The metal pattern may form an encoding pattern as well as a separate align key at a preset location to facilitate the alignment with a photoconversion pattern that will be formed later.
Subsequently, the metal pattern is transferred to an adhesive film to manufacture the adhesive film having a metal pattern layer (step b).
The adhesive film can easily separate from the metal pattern layer by an external force or heat, and may be an adhesive tape or a thermal release tape. The adhesive film may cap the structure per se, and after detached, the adhesive film may form a separate capping structure.
A pattern matching to the align key formed at the step (a) may be transferred to the adhesive film together, to facilitate the alignment with a photoconversion pattern that will be formed later.
The step for removing graphene transferred to the adhesive film having the metal pattern layer may be additionally performed.
The adhesive film having the metal pattern layer itself may be used as an adhesive film having a plasmonic effect. Accordingly, the metal pattern layer may be transferred to a target device, and the adhesive film alone may be detached according to necessity.
Subsequently, a metal substrate is prepared (step c).
The metal substrate may have imprint matching to the align key formed in the adhesive film.
The metal substrate may be of a 2D metal thin film type, and may be at least one metal selected from noble metal materials having low absorption loss in the metal itself, such as gold (Au), silver (Ag) and copper (Cu), or alloy containing at least one metal as a main component.
The thickness of the metal substrate is preferably 10 nm or more to obtain a sufficient gap plasmon polariton effect while blocking visible light penetration.
Subsequently, a photoconversion pattern including photoconverting nanoparticles is formed on the metal substrate to manufacture the substrate having a photoconversion pattern layer (Step d).
The photoconversion pattern (corresponding to pattern B) may be formed by patterning with the alignment to the imprint matching to the align key on the metal substrate to form an overlapping part with the metal pattern.
The photoconversion pattern may be formed by photo lithography, electron beam lithography, X-ray lithography, ion beam lithography and soft lithography, but the scope of the present disclosure is not limited thereto.
A gap plasmon polariton phenomenon may take place between the metal substrate and the metal pattern.
Finally, the adhesive film having the metal pattern layer is placed on the substrate having the photoconversion pattern layer, to form a visible pattern area (corresponding to pattern C) which is the overlapping part between the photoconversion pattern layer and the metal pattern layer (Step e).
A photoconversion amplification phenomenon may take place at the visible pattern area when infrared light is applied.
Subsequently, it is preferable to additionally perform the step for removing a transferred part of the pattern matching to the align key of the adhesive film. When the align key is removed, it is practically impossible to re-assemble in the event that the structure is deformed, thereby preventing the reuse of the structure.
The present disclosure provides a packaging box or container for preventing counterfeit, falsification or reuse comprising the structure.
The structure may be mounted on the surface or an opening of the packaging box or container.
The present disclosure provides a method for discriminating counterfeit, falsification or reuse.
Specifically, first, infrared light is applied to the structure for preventing counterfeit, falsification or reuse according to the present disclosure (Step 1).
Subsequently, counterfeit, falsification or reuse of the structure is discriminated by identifying a light emission pattern appearing on the structure to which the infrared light is applied (Step 2).
The discrimination may be performed by identifying the light emission pattern (corresponding to pattern C of
The method for discriminating counterfeit, falsification or reuse according to the present disclosure should be selectively used according to the purpose. That is, to discriminate counterfeit, falsification and reuse more accurately, a method which compares and analyzes the light emission intensity of visible light and the shape of the spectrum using a visible light detection device may be used.
Hereinafter, the present disclosure will be described in further detail through example, but the following example should not be construed as reducing or limiting the scope and the content of the present disclosure. Furthermore, based on the disclosure of the present disclosure including the following example, it is obvious that those skilled in the art could easily practice the present disclosure not presenting specific experimental results, and it is also obvious that these variations and modifications fall within the appended claims.
Furthermore, the experimental results presented below describe only representative experimental results of example and comparative example, and each effect of many embodiments of the present disclosure not providing an explicit statement below will be specifically described in the corresponding section.
In this instance, to prevent an adverse influence of graphene on a device, O2 plasma surface treatment is performed over graphene for a few seconds to remove graphene. Furthermore, in case that a thermal release tape is used instead of the adhesive tape, only the Ag nanoparticles may be transferred to a target device. The typical application temperature of the thermal release tape is around 100° C., and when this transfer method is used, it is advantageous in applying to a polymer device that should avoid chemical treatment or is vulnerable to high temperature treatment.
First, a SiO2 substrate to which graphene has been transferred was prepared, and a metal electrode pattern was formed on graphene through electron beam lithography. A thermal release tape was attached onto the formed metal pattern and then detached, so that the metal pattern was transferred to a tape surface. In this instance, an unnecessary graphene part was removed by performing O2 plasma surface treatment for a few seconds. Subsequently, after alignment was performed on target polymer arrays, the thermal release tape was attached properly to a target location. Here, in this condition, capping with the thermal release tape may be performed, and in this case, a separate sealing process may be omitted. Alternatively, when necessary, the thermal release tape may be peeled off by applying weak heat, and a separate sealing process may be performed.
For pattern A, a silver (Ag) pattern film of 10 nm in thickness was formed on graphene/SiO2 through patterning as in Manufacturing Example 2, a dewetting process was performed as in Manufacturing Example 1, and the processed silver (Ag) nanoparticle pattern was transferred to an adhesive tape, to manufacture the adhesive film having the silver pattern.
For pattern B, an Ag thin film substrate on which an incision has been created in the shape of an align key (not shown) was prepared. An Ag thin film was formed by forming a Ti adhesive layer on a silicon substrate with the thickness of 20 nm, and depositing Ag to prevent the Ag thin film from being separated from the substrate. An intaglio photoresist (PR; SU-8) pattern in the shape of pattern B was formed on the Ag thin film by patterning with the alignment to the align key, photoconversion nanoparticles (β-NaYF4:Yb3+/Er3+) up-converting (IR to VIS) and having the average diameter of 20 nm were coated, and spin coating was performed at 3000 rpm for 30 seconds to manufacture a pattern layer of an photoconversion nanoparticle monolayer having a uniform thickness. In this instance, chloroform which is a solvent used in the coating process of photo-conversion nanoparticles is fully volatilized during spin coating, and thus a drying process was not performed.
After a lift-off process is completed, pattern B of the photoconverting material of about 20 nm in size cannot be identified with an eye, and it is very difficult to identify the pattern even under a microscope.
When the transfer tape having the metal pattern layer with pattern A and the silver substrate having the photoconverting pattern with pattern B are aligned to the align key, a plasmonic structure of metal particle-photoconverting material-metal film is formed only at the location of real pattern C, leading to amplification of photoconverting light emission, while at the remaining area, only photoconverting material-metal film structure is formed, reducing light emission, or a metal particle-metal film structure is formed, failing to emit light due to the absence of a light emitting material.
In this instance, if the align key on the top of the tape is removed, even though the structure is deformed and then re-attached, alignment becomes difficult. Furthermore, in case that attaching and detaching repeats in the attempt of re-attaching, secondary damage may occur to the photoconverting material by the adhesive of the tape, making recovery more difficult.
A structure was manufactured by the same method as Example 1 except that for a metal substrate, a glass substrate was used instead of a silver (Ag) thin film.
A structure was manufactured by the same method as Example 1 except that an photoconverting pattern was formed using a glass substrate for a metal substrate instead of a silver (Ag) thin film, and a process for attaching an adhesive tape with silver nanopattern was omitted.
A structure was manufactured by the same method as example 1 except that a process for attaching an adhesive tape with silver nanopattern was omitted.
Near-Infrared Light (980 nm) Up-Converting (Photoconversion) PL Spectra Analysis
According to
Moreover, it was found that the structure of Comparative Example 3 reduced in light emission intensity due to a quenching effect.
Furthermore, the structure of Comparative Example 2 has a surface plasmon effect due to the presence of the metal pattern layer, but nevertheless, because of a structure with no metal substrate, it showed similar light emission intensity to the structure of Comparative Example 3.
That is, it can be seen that the structure according to the present disclosure emits visible light being identifiable with an eye when infrared light is applied, because of a gap plasmon polariton effect occurring in the gap between the metal pattern layer and the metal substrate.
Consequently, it can be seen that when the two encoded patterns are separated, the structure according to the present disclosure remarkably reduces in the intensity of visible light emitted and the visible pattern of the structure is not identified with an eye, and through this, it is possible to identify whether the structure according to the present disclosure is counterfeited, falsified and reused.
While the embodiments of the present disclosure have been hereinabove described, various modifications and changes may be made to the present disclosure by those having ordinary skill in the art with supplement, alternation, deletion or addition of the elements without departing from the spirit of the present disclosure defined in the appended claims, and these modifications and changes fall within the scope of protection of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2017-0093746 | Jul 2017 | KR | national |
| 10-2017-0103997 | Aug 2017 | KR | national |
| Number | Name | Date | Kind |
|---|---|---|---|
| 8216872 | Shieh | Jul 2012 | B1 |
| 20100307705 | Rahm | Dec 2010 | A1 |
| 20160190370 | Ko | Jun 2016 | A1 |
| Number | Date | Country |
|---|---|---|
| 10-2009-0092278 | Aug 2009 | KR |
| 10-2011-0045194 | May 2011 | KR |
| 10-2012-0116635 | Oct 2012 | KR |
| WO 2017090831 | Jun 2017 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20190023044 A1 | Jan 2019 | US |
