OPTICAL DEVICE WITH ORDERED SCATTERER ARRAYS FOR SECURE IDENTITY AND A METHOD OF PRODUCING THE SAME

Abstract

An optical device with ordered scatterer arrays for secure identity and a method of producing the same

This invention discloses a method for configurable spatial control and modification of optically active resonantly coupled scatterer arrays to produce identifiable security features and a corresponding photonic secure identity device. The invention comprises at least the steps of (i) producing a deposition template from said master stamp, (ii) synthesis of a plasmonic particle colloid, (iii) producing an optically active, two-dimensional security tag template using self-assembly of said particles on said deposition template, (iv) producing a customized secure identity device from said security tag template by selective removal or modification of optical properties using ultrashort laser pulses. The produced customized plasmonic-photonic device can then be used as secure identity and anti-counterfeiting means. The device exploits customized spatial control and modification of optically active plasmonic particle arrays demonstrating surface lattice resonance optical signature to produce easily identifiable security features.

Claims

1. A secure identity optical device for anti-counterfeiting measures which is configured to produce visually (801, 902, 1004, 1103), spectroscopically (701), and/or microscopically (102, 103, 801, 902) verifiable security features wherein the optical device comprises at least: a substrate (201); and a plurality of optical scatterers (101, 202) affixed onto the substrate (201) and separated from adjacent scatterers (202) by a distance to form a two-dimensional pattern; characterized in that said optical scatterer pattern comprises at least one of: a) a specifically designed binary pattern (102, 105, 104, 801, 1003, 1101), wherein some scatterers either are (202) or are not (204) in a selected location on the substrate; b) a specifically designed colour-based pattern (103, 902), wherein some scatterers (902) scatter a measurably different colour of light compared to adjacent scatterers (901); c) a specifically designed photonic interaction between said scatterers (202), wherein said interaction results in features in an optical spectrum (701); or d) a combination thereof in any proportion.

2. The device of claim 1, wherein said scatterer pattern comprises at least one of: a) a varying distance between adjacent scatterers (202, 601); or b) a plurality of non-single optical scatterer arrangements, specifically, absence of a scatterer (204), dimers (205), trimers, tetramers, or higher order multi-scatterer arrangements (601).

3. The device of claim 1, wherein said scatterer pattern is configured to produce a Rayleigh anomaly upon illumination with electromagnetic radiation and the electric dipole and/or quadrupole of the optical scatterers overlaps said Rayleigh anomaly to produce a surface lattice resonance (SLR) (701).

4. The device of claim 1, wherein said binary pattern constitutes a computer-generated hologram (1003) of an image (1002), which can be reconstructed in the far-field by monochromatic illumination (1004).

5. The device of claim 1, wherein said binary pattern constitutes an array of finite sized areas each comprising lines of scatterers (holo-pixels) (1101) and said holo-pixel array produces a visual holographic image (1103).

6. The device of claim 1, further comprising a transparent superstrate material (1201) secured on top of the substrate (1203) and enclosing said scatterers (1202) underneath.

7. A method of producing the device of claim 1, comprising steps of: providing a substrate (201) with an array of obstacles (203), the substrate being produced by any means of standard nanofabrication routes; synthesizing a colloid solution (402) comprising monodisperse scatterers (403); depositing the colloid solution (402) onto the substrate (404) with an array of obstacles (407) wherein self-assembly of said scatterers (403) occurs on said deposition substrate.

8. The method of claim 7, further comprising a step of depositing one or more transparent protective layers (1201) on top of the substrate (1203).

9. A method of creating a customized binary pattern on the device of claim 1, comprising steps of: providing a substrate (1303) with an array of scatterers (1302); providing one or more laser beams (1301) of monochromatic light radiation; providing optomechanical means to focus at least one laser beam (1301) onto the surface of said substrate (1303); translating the substrate (1303) or/and positioning of the focused laser spot (1301) over defined places of said substrate (1303); providing means of controlling the laser patterning process; focusing a laser spot energy density such that energy is selectively transferred into the scatterers (1302) to increase the local temperature of the scatterers (1302) thereby causing any one of: selective reshaping, fracturing, coalescence, removal of said scatterers (1302), or any combination thereof; and repeating the penultimate step a plurality of times for a plurality of spots in different locations of the substrate (1303) to define a custom pattern (102, 103, 104, 801, 902, 1003).

10. The method of claim 9, wherein the light radiation is provided in the form of two or more laser beams (1402) that are spatially and temporally overlapped and concentrated into a single spot on the surface (1403) by means of directing and focusing optics and form an interference pattern (1401) with a laterally varying intensity with some periodicity.

11. The method of claim 10, wherein the periodical intensity pattern is controlled by using any of the following: varying the number of interfering beams (1402) to control the spatial configuration of the intensity pattern (1401); varying the phase and/or the polarization of each beam (1402), to control the spatial configuration of the intensity pattern (1401); varying the angle between interfering beams (1402), to control the pitch of the pattern (1401); varying the orientation of the interference pattern (1401).

12. The method of claims 9, wherein said scatterers (1302, 1403) or their groups are selectively affected, to form a binary pattern (102, 105, 104), a colour-based pattern (103), or combinations thereof in any proportion, by one or several of steps: removal so that the array of scatterers (1302, 1403) loses a scatterer or a group thereof; reshaping so that the array of scatterers (1302, 1403) locally changes the central wavelength of scattered electromagnetic radiation; fracturing into smaller scatterers so that said array (1302, 1403) gains new scatterers having shifted central wavelength of scattered electromagnetic radiation; and coalescing into bigger scatterers so that the array of scatterers (1302, 1403) locally changes its central wavelength of scattered electromagnetic radiation.

13. The method of claim 9, wherein the irradiation using multiple beams (1402) is used to impose a system of diffraction gratings comprising a decorative pattern where each separate spot contains a predefined pattern imposed in the two-dimensional scatterer array (1101), thereby the overall system forms a dot-matrix hologram (1102).

14. The method of claim 9, wherein the irradiation is used to spatially alter the array of scatterers (1302, 1403) to form binary patterns comprising any combination of: a microtext, a nanotext, or any combination thereof (102); a two-dimensional binary image (801); a Computer-Generated Hologram (104, 1003) of an image (1002); and an array of larger pixels comprising lines of scatterers (105, 1101) forming a dot matrix hologram (1102).

15. A method of verifying the device of claim 1, comprising any steps of: verifying the signatures in the optical spectra (701), verifying the binary or colour image or text seen through an optical microscope under dark-field illumination (102, 103, 105, 501, 801, 901);, verifying the dot-matrix hologram by a naked eye under white-light illumination (1103), verifying on a screen when the computer-generated hologram is illuminated using monochromatic visible light (1004), or verifying by any combination of above steps, depending on the customizations imposed in the device.

Description

DESCRIPTION OF DRAWINGS

[0021] The drawings are provided as a reference to possible embodiments and are not intended to limit the scope of the invention. Neither of the drawings and graphs presented herein should be construed as limiting the scope of the invention, but merely as an example of a possible embodiment.

[0022] FIG. 1 shows a customized regular scatterer array by this invention.

[0023] FIG. 2 shows a regular scatterer array arranged in a rectangular pattern with unique defects.

[0024] FIG. 3 shows a process to fabricate a patterned substrate (also known as deposition template) for the security tag.

[0025] FIG. 4 shows the deposition method to produce a security tag template, where a drop of colloidal solution confined by a glass cover slide is slowly translated over a temperature-controlled substrate with size-matched obstacles. Horizontal arrow indicates the direction of translation.

[0026] FIG. 5 shows a dark field optical microscope micrograph of a scatterer array.

[0027] Scale bar 20 μm

[0028] FIG. 6 shows a scanning electron microscope micrograph of a scatterer array. Scale bar 5 μm

[0029] FIG. 7 shows a visible transmission spectrum of a scatterer array comprising a characteristic broad LSPR dip, position of the RA and a narrow SLR dip.

[0030] FIG. 8 shows a dark field optical microscope micrograph of a customized scatterer array with a monochrome image. Scale bar 20 μm.

[0031] FIG. 9 shows a dark field optical microscope micrograph of a scatterer array with a colour-based customization, where different grey scale values represents different colours.

[0032] FIG. 10 shows a computer-generated hologram generated from an image of a letter “P”, a dark field optical microscope micrograph of a laser customized scatterer array with computer-generated hologram (scale bar 20 μm), and laser imposed CGH reconstruction from a customized scatterer array on a screen using illumination from a green laser pointer (scale bar 100 mm).

[0033] FIG. 11 shows a dark field optical microscope micrograph of a customized scatterer array after irradiation with two laser beam interference fringes. Multiple holo-pixels forming a dot-matrix hologram are seen (scale bar 20 μm), a camcorder image of the same dot matrix hologram diffraction under different illumination conditions when the background around the letter “A” is diffracting light towards the observer, and a camcorder image of the dot matrix hologram diffraction when the letter “A” is diffracting light towards the observer (scale bar 2 mm).

[0034] FIG. 12 shows a customized scatterer pattern with a protective transparent cover.

[0035] FIG. 13 shows a nearly diffraction limited focused laser beam irradiation used for customization of a scatterer array. Arrows indicate the option to scan either the sample or the beam.

[0036] FIG. 14 shows a scheme for patterning subwavelength regular patterns on a scatterer-containing template utilizing holographic lithography.

DETAILED DESCRIPTION OF INVENTION

[0037] A security tag comprises at least two features that are essential: a substrate (201) and a plurality of optical scatterers (202) affixed to said substrate. The task of identification and anti-counterfeiting protection with added levels of security that are advanced over the prior art is achieved by a unique arrangement of said optical scatterers and by the possibility of complete removal or modification of their properties in relation to each other. Effects generated by this device are impossible to fake and are verifiable either visually, by means of microscopy, by means of spectroscopy, or any combination thereof depending on the features included in the device.

[0038] In one of the possible embodiments of the invention, the substrate could comprise technological superficial features composed in a pattern, e.g., identical pits (203), that are essential for template-assisted particle deposition methods. The initial uniqueness of every tag can then be achieved by using a self-assembly technique, wherein the optical scatterers are made to closely follow the physical pattern on the substrate, but in such a way that some randomness is maintained by some scatterers not falling in their predefined positions and leaving them empty (204). Additionally, the holes can be larger than the lateral dimension of the particle, which introduces slight positional randomness in every pit (202, 601). Furthermore, if the traps are sufficiently large (or the scatterers are sufficiently small), some pits could randomly acquire more than one scatterer (205, 601).

[0039] In one embodiment, the substrate with superficial features could be provided by means of standard nanofabrication routes, e.g., electron beam lithography, dry etching, and soft lithography. A standard technique involves cleaning a silicon wafer (302), spin-coating a layer of electron/photosensitive/nanoim print resist layer (301), pre-processing according to manufacturer instructions, and exposing (303) and developing a pattern (304) for optical scatterers to eventually follow. In this case, the substrate is the resist layer (304), and the superficial features are the resulting developed structures.

[0040] In a different embodiment, the pattern can be transferred to a different material, e.g., silicon, by an additional etching step of the wafer (305) using a variety of different dry etching recipes. To efficiently produce holes in silicon using negative-tone resist and e-beam lithography, an additional lift-off step is required with a thin metal layer, e.g., A1, to produce a hard mask. If dot-exposure is used with a positive-tone resist, the polymer mask itself can be used as an etching mask. In the embodiments discussed herein, an ion-assisted SF.sub.6 plasma etching with a passivating gas (C.sub.4F.sub.8), or a cryogenic etch at −120° C. and SF.sub.6/O.sub.2 plasma is used. In this case, the substrate is a patterned silicon wafer (306).

[0041] In another embodiment, the substrate could comprise a polymer substrate made using soft lithography by replicating a silicon (or other material) master mould produced by the steps described above. The produced master stamp (306) should preferably be coated with a self-assembled monolayer of FDTS as an anti-adhesion coating. The replica of the inverse relief of the silicon master is made in polydimethylsiloxane by means of soft lithography (307). 10:1 mixture of prepolymer and curing agent is mixed per manufacturer (Sylgard) instructions and degassed in a vacuum chamber. The mixture is poured over the silicon mould and a cover slip is placed on top to help spread it evenly and later provide a rigid substrate for the replica. The stack is cured at a temperature and for a period described in the manufacturer instructions. The patterned replica mould (308) is then separated by peeling it off together with the cover slip and serves as the substrate.

[0042] The task of optical scatterers in an embodiment of the invention is to scatter light with some dependency to wavelength, i.e., to produce a colour. The properties of scattering depend on the size and shape of the scatterers and the dielectric functions of the scattering (202) and the surrounding (201) material; both metal and dielectric materials can be used. In one embodiment, said scatterers could be plasmonic nanoparticles made of Ag. Silver nanoparticles having the LSPR in the visible or /and NIR wavelength range can be synthesised using wet chemistry methods aiming at high monodispersity. Monodisperse spherical silver nanoparticles can be synthesized using seeded-growth approach as by Neus G. Bastus et al. [4]. The variation of the concentration and ratio of the precursors allows to synthesize 20-270 nm nanoparticles with a tight deviation in diameter. Alternatively, particles of different geometry can be synthesized using the polyol synthesis route as by Andrea Tao et al. [3].

[0043] In an embodiment of the invention the optical scatterers could be made to follow a defined pattern by affixing them to some or all described substrate features via a self-assembly type method such as capillary force assisted particle assembly (FIG. 4). A drop of the colloidal solution (402) is confined between a stationary glass slide (401) and the patterned substrate (404). The substrate is held at a predefined temperature (406) and translated at a predefined speed towards the indicated direction (405). The order of nanoparticles (403) matches the pattern defined, but unique randomness is maintained by deposition defects (601) (e.g., unfilled pits (204), multiple particles per pit (205)) and positional/orientation randomness (i.e., if the particle is smaller than the hole). The depth of the holes is related to the size of the optical scatterers and should be on the same order of magnitude to maintain the overall majority of single particles per pit. Typical deposition conditions are 0.1-10 μm/s translation speed and 10° C. above the atmospheric dew point. Typically, the highest stable concentration can be used. An embodiment produced according to this example will have an arbitrary assembly yield, therefore featuring a unique nanoparticle pattern (501, 601) that can already be used as an anti-counterfeiting feature, because no two depositions can be the same, and a designated verification area could be verified via microscopy.

[0044] In some embodiments of the invention, substrate sheets with the scatterers already arranged or produced by industrial processing can be available for users to customize by laser processing and produce secure identity and anti-counterfeiting tags.

[0045] One more embodiment of the invention comprises optical scatterers that are separated from adjacent optical scatterers to form a regular pattern (501, 601), such as a square lattice, rectangular lattice, triangular lattice, or any other two-dimensional lattice that can be defined by a unit cell and some periodicity. This opens the way to produce substrates (201) with said superficial features by parallel lithography means, such as holographic lithography.

[0046] Additionally, the introduction of regularity in the pattern allows a condition called Rayleigh anomaly (RA). It is a condition for light to diffract in the plane of the periodic features, and the energy of light fulfilling this condition can be calculated by

[00001]$\begin{array}{cc}E=\frac{\hslash c}{n}.Math.{\stackrel{.fwdarw.}{k}}_{//}+\stackrel{.fwdarw.}{G}.Math.,& \mathrm{Equation}\left(1\right)\end{array}$

where Ε is the energy of RA, —reduced Planck's constant, c—speed of light in vacuum, n—refractive index of the medium the nanoparticles are embedded in, k.sub.II—in plane projection of the wavevector (for normal incidence equals 0), and G—the grating vector. The scattering spectrum of the optical scatterers could overlap this RA energy and produce a phenomenon called surface lattice resonance (SLR), which features narrow extinction peaks, and therefore a security tag possessing the surface lattice resonance will have an additional security feature verifiable by means of UV-vis-NIR spectrophotometry. In one more of the embodiments, the localised surface plasmon resonance (LSPR) of plasmonic nanoparticles centred at 500 nm with a FWHM of 100 nm and overlapping an RA at 600 nm could generate an SLR (701). To design this kind of security feature, the designer needs to either know the scattering signature before designing the substrate pattern (and defining the RA energy as a consequence), or vice versa. The optical scattering characteristics can be obtained analytically before producing the pattern, i.e., through modelling and/or analytical solutions, such as FEM and using the Mie solution for optical scatterers, or experimentally after synthesis, using standard UV-vis-NIR spectrophotometry techniques.

[0047] Regardless of the type of pattern, the optical scatterers could be further modified by selectively and intentionally changing the scattering signature or removing some of them to produce additional, custom, unique, and verifiable features. The modification can be binary, i.e., the scatterer either is or is not affixed to the substrate in a defined location, or continuous, i.e., the scatterer can have a different scattering signature compared to adjacent scatterers.

[0048] In one more embodiment of the invention, the optical scatterers could be arranged in a custom way so that the overall binary (801) or continuously varying colour pattern (902) would constitute a larger visually or microscopically identifiable image and/or text (102, 103). An example of a binary image of a tree is observable through an optical microscope because the nanoparticles were selectively removed (801). An example of a colour-based modification is observable through an optical microscope because the nanoparticles were selectively reshaped (902). The customization can include different size and/or font letters, linear and/or matrix bar codes, mathematically defined curves, and other graphical information.

[0049] Additionally, the binary pattern (1003) could constitute a computer-generated hologram (104, 1001) of an image (1002). In this embodiment of the invention, the validity of the anti-counterfeiting tag could be verified by shining monochromatic light onto the tag and observing a far-field image (1004) that was encoded by the Iterative Fourier transform algorithm using not less than 100 cycles.

[0050] Moreover, the binary pattern could constitute optical scatterers arranged in periodic lines and confined in defined areas, holo pixels (105, 1101). A large array of such areas with different orientations and periodicities of these lines can produce a dot matrix hologram (1102). Upon illumination with white light, holographic rainbow effect with an encoded image is observed (1103).

[0051] Finally, an embodiment of the invention could have an additional layer of transparent material (1201), such as a transparent polymer PDMS, to increase the robustness of the device while maintaining the colours produced by the optical scatterer pattern (1202). In one example, the described PDMS prepolymer mix could be poured directly on the substrate (1203) with pristine or customized optical scatterers (1202) and be left to cure. This process should be the last step of the production, regardless of the type or complexity of the device disclosed herein.

[0052] An embodiment of the method to produce binary (102, 104, 105, 801, 1003, 1101) or colour-based (103, 902) patterns can be carried out by femtosecond laser irradiation with a high numerical aperture objective and precise translation with a motorized three-axis stage with respect to the focus of a stationary, nearly diffraction limited laser beam focused (1301) on scatterer arrays (1302) on a substrate (1303). Alternatively, the laser beam can be scanned over the scatterer array on a substrate, e. g., employing a galvanometer scanner and/or laser head translation. Laser modification threshold is reduced by selecting a wavelength close to the extinction cross-section peak of the optical scatterers, therefore improving the probability of interaction. Multiple photon absorption is also possible when ultrashort pulses are used.

[0053] The interaction of light with free-standing optical scatterers induces several effects depending on the energy density and the number of optical scatterers in the vicinity. Firstly, scatterers can remelt, lose their initial form, and translate into spheroids. Secondly, the scatterers can combine to form bigger structures or fracture into smaller ones. These two effects contribute to colour-based patterning (902). Finally, they can be removed from the substrate completely. The latter is useful when forming binary patterns (801). In our embodiment, 15 mJ/cm.sup.2 range fluence is provided by irradiation with the second harmonic (515 nm) of 270 fs pulse length Yb:KGW laser. Local changes of size-related light scattering properties can be seen using dark field optical microscopy. The customization through binary or colour-based patterns with a single focused laser beam (1301) is limited by the spot size of the focused laser beam. If the spot size is larger than the interparticle distance of the optical scatterers, more than one scatterer may be affected.

[0054] A computer-generated hologram (1001) can be calculated using an iterative Fourier transform algorithm and imposed on the scatterer array as a binary pattern (1003). The pattern is visible using a microscope, but it is only understandable through a mathematical 2D Fourier transformation; or when it is illuminated by a laser. The encoded image is then visible on a screen (1004) with a naked eye.

[0055] Two or more interfering coherent laser beams (1402) can be used to form periodic interference fringes (1401) instead of diffraction limited spot size (1301). When two beams are used, the pitch of the grating can be calculated by

[00002]$\begin{array}{cc}\Lambda =\frac{\lambda }{2}/\sin \left(\frac{\theta }{2}\right),& \mathrm{Equation}\left(2\right)\end{array}$

where Λ is the pitch of a grating, λ is the wavelength of interfering light, θ is the angle between the two interfering beams. More complex two-dimensional interference patterns are available when more than two laser beams are interfering and the phase difference and/or polarization of the beams is varied in a controlled fashion by introducing additional optical paths and waveplates, respectively. Irradiating the scatterer arrays (1403) on a substrate (1404) results in selective removal of scatters along periodically repeated high intensity areas (interference fringes, 1401). Usually, rectangular or oval areas are affected (1101) depending on the beam intensity distribution. By tailoring the periodicity and the angle of the interference fringes (1401) in the XY plane, one can construct an array of closely spaced holo-pixels and form a dot-matrix hologram (105, 1102). The dot-matrix holograms formed by customized optical scatterer arrays diffract light in a designed fashion that can be seen by the naked eye (1103).

NON-PATENT LITERATURE

[0056] 1 Marcus S. Carstensen, Xiaolong Zhu, Oseze Esther Iyore, N. Asger Mortensen, Uriel Levy, Anders Kristensen, Holographic Resonant Laser Printing of Metasurfaces Using Plasmonic Template. ACS Photonics 2018, 5, 1665-1670, https://doi.org/10.1021/acsphotonics.7b01358

[0057] 2 Shikai Denga, Ran Li, Jeong-Eun Park, Jun Guan, Priscilla Choo, Jingtian Hu, Paul J. M. Smeets, Teri W. Odom, Ultranarrow plasmon resonances from annealed nanoparticle lattices. PNAS 2020, vol. 117 No. 38 23380-23384 https://doi.org/10.1073/pnas.2008818117.

[0058] 3 Andrea Tao, Prasert Sinsermsuksakul, and Peidong Yang, Polyhedral Silver Nanocrystals with Distinct Scattering Signatures. Angew. Chem. Int. Ed. 2006, 45, 4597-4601, https://doi.org/10.1002/anie.200601277.

[0059] 4 Neus G. Bastus, Florind Merkoci, Jordi Piella, and Victor Puntes, Synthesis of Highly Monodisperse Citrate-Stabilized Silver Nanoparticles of up to 200 nm: Kinetic Control and Catalytic Properties. Chem. Mater. 2014, 26, 2836-2846. https://doi.org/10.1021/cm500316k.