This application is the U.S. National Stage of International Application No. PCT/EP2008/010747, filed Dec. 17, 2008, which claims the benefit of German Patent Application DE 10 2007 061 979.2, filed Dec. 21, 2007, both of which are hereby incorporated by reference to the extent not inconsistent with the disclosure herewith.
The present invention relates to a security element for security papers, value documents and the like having a feature region that selectively influences incident electromagnetic radiation. The present invention further relates to a method for manufacturing such a security element, as well as a security paper and a data carrier having such a security element.
Holograms, holographic grating images and other hologram-like diffraction patterns have been in use for several years to ensure the authenticity of credit cards, banknotes and other value documents. Today, metalized embossing holograms that preferably consist of sinusoidal surface profiles having grating periods between about 600 nm and 2 μm serve on countless banknotes as a sign of their authenticity.
To further improve the attractiveness and counterfeit security, a number of optically variable effects were developed: as soon as the banknote is moved relative to the viewer and/or to the light source, the hologram drastically changes its appearance. Color changes that manifest themselves in so-called moving, tilt or morph effects are particularly typical. This optical variability and the metallic gloss of the metalized hologram foils ensure that true banknotes clearly differ from counterfeits that were created with the aid of color printers. Comparable optical variability cannot be achieved with commercially available inks. Diffraction gratings, the basic building blocks of such holograms, produce, in principle, a spectral color split.
Despite the high level of development that the holograms used to protect banknotes against counterfeiting have since reached, ever-better counterfeits are reaching the market. The grating periods of at least 600 nm used in the holograms are manufacturable not only with electron beam lithography systems, but also through interferometric direct exposure with the aid of a laser, which significantly reduces the counterfeit security of the holograms. Hologram counterfeits are particularly frequently made with the aid of dot matrix systems, whose operating principle is ultimately likewise based on the interference of laser beams.
Also so-called moiré magnification arrangements have been in use for some time as security features. The fundamental operating principle of such moiré magnification arrangements is described in the article “The moiré magnifier,” M. C. Hutley, R. Hunt, R. F. Stevens and P. Savander, Pure Appl. Opt. 3 (1994), pp. 133-142. In short, according to this article, moiré magnification refers to a phenomenon that occurs when a grid composed of image objects is viewed through a lens grid having approximately the same grid dimension. As with every pair of similar grids, a moiré pattern results, each of the moiré strips in this case appearing in the form of a magnified and rotated image of the elements of the image grid.
Due to the small line width of about a micrometer of the letters and symbols used in such moiré magnification arrangements, it was not previously possible to produce colored letters through finely patterned metallic surfaces. Diffraction effects may hardly be considered for the coloring because gratings having the usual periods cannot be accommodated in the lines of which the letters or symbols of the micropattern array consist, or can be accommodated only in special cases.
Furthermore, the lens array used for viewing evens out the angle split of individual spectral colors, such that classical grating diffraction in the first diffraction order is little suited for coloring in moiré magnification arrangements or in the more general modulo magnification arrangements.
Based on that, the object of the present invention is to avoid the disadvantages of the background art and especially to create a security element having an attractive visual appearance and high counterfeit security.
This object is solved by the security element having the features of the main claim. A method for manufacturing such a security element, a security paper and a data carrier are specified in the coordinated claims. Developments of the present invention are the subject of the dependent claims.
According to the present invention, in a generic security element is provided that the feature region includes metallic nanopatterns in which volume or surface plasmons are excited and/or resonance effects are caused by the incident electromagnetic radiation.
Plasmons are collective oscillations of the free electrons relative to the ion cores in metals. An increased absorption of the excitation light occurs at the so-called plasma frequency. Light scattering can occur through recombination of plasmons in radiation, especially if the metal is present in particle form. Surface plasmon polaritons (SPs) are electromagnetic radiation that is bound to metallic interfaces and that propagates along its boundary layer, and in doing so, suffers absorption. The excitation of surface plasmon polaritons occurs via the adaptation of the momentum of the incident light and the surface plasmon polaritons via a dielectric or via the reciprocal grating vector of the periodic patterning of the metal surface.
Further, exceptional intensity changes in the transmission or in the reflection can occur at subwavelength gratings if the incident light leads to resonances in the interstices or in the cavities in the grating pattern. Also such resonance effects can be explained by the excitation of surface plasmons or surface polaritons by the incident radiation. Here, in transmission gratings, one can observe a strong intensity shift between reflection and transmission for certain wavelength ranges. These so-called cavity resonances likewise lead to an increased absorption of the light. It is worth mentioning that this effect can also induce an exceptional transmission increase.
Even if the cited physical effects are currently considered to be the correct description of the occurring phenomena, the present invention is defined by the spatial-physical embodiment of the proposed security elements and is not bound to the given explanation of the phenomena due to excitation of volume or surface plasmons or the occurrence of resonance effects.
In the context of the present invention, it is preferred when the feature region of the security element selectively influences incident electromagnetic radiation in the visible spectral range. In particular, the feature region can selectively reflect and/or transmit incident electromagnetic radiation. For example, the feature region can reflect certain spectral portions of visible light and transmit other spectral portions of visible light and, in this way, appear having different colors in reflection and transmission.
To develop a see-through security element, the feature region can especially be developed to be transparent or translucent. In security elements that are designed for viewing in reflection, the feature region or the substrate of the security element can also be opaque.
The feature region can include different metallic nanopatterns in different sub-regions, for example to produce different-colored regions within the security element.
In a preferred variant of the present invention, the feature region exhibits, as metallic nanopatterns, metallic nanoparticles that are embedded in a carrier medium. The metallic nanoparticles advantageously exhibit a largest dimension between 2 nm and 400 nm, preferably between 5 nm and 300 nm, and particularly preferably between 10 nm and 200 nm.
The metallic nanoparticles can be developed to be substantially spherical, but they can also be developed having a preferred direction, especially as rotation ellipsoids or in the shape of rods or platelets.
In an advantageous embodiment, the metallic nanoparticles are formed from homogeneous metallic particles, especially from Au, Ag, Cu or Al particles, since with these, the described color effects are observable in the visible spectral range. In addition, also other metals may be considered, such as Ni, Cr, Wo, Vd, Pd and Pt, as well as alloys of one or more of the cited metals. Alternatively, the metallic nanoparticles can be formed from core-shell particles in which one of the materials of the core and shell is a metal, especially Au, Ag, Cu, Al, another of the above-mentioned metals, or a metal alloy. The other of the materials of the core and shell is advantageously likewise a metal or a dielectric.
To be able, after the application, to arrange or align the nanoparticles through a magnetic field, it can be provided that one of the materials of the core and shell is magnetic. The feature region can further include a mixture of different metallic nanoparticles, especially a mixture of nanoparticles of different diameters.
In the context of the present invention, the carrier medium is preferably formed by a transparent or colored lacquer layer.
In one development of the present invention, the feature region exhibits a patterned surface having elevations and depressions, the metallic nanoparticles being arranged in the depressions of the patterned surface. The patterned surface can especially be formed by a thermoplastically embossable material or an embossed lacquer layer, especially an embossed UV lacquer layer. In some embodiments, the patterned surface is expediently metalized.
To combine the color effects of the nanoparticles with diffraction effects, the patterned surface can form a diffraction pattern that splits the incident electromagnetic radiation spectrally.
Depending on the desired color effect, the patterned surface can be developed to be periodic or also stochastic in one or two spatial directions.
The feature region can further include a metal layer over which the metallic nanopatterns are arranged. In one development of the present invention, the feature region includes a thin-film element that has a color-shift effect and exhibits a metal layer, an absorber layer and a dielectric spacing layer arranged between the reflection layer and the absorber layer, the metallic nanoparticles being arranged in the dielectric spacing layer. The metal layer can be developed to be reflective or, in the event that the security element is to be looked through, also semitransparent.
According to a further, likewise advantageous variant of the present invention, the feature region includes, as metallic nanopatterns, one or more subwavelength gratings having grating periods below the wavelength of visible light. The subwavelength gratings can be developed, for example, as binary patterns that include exclusively planar metallic areal sections on only two different height levels, or as multilevel patterns that include exclusively planar metallic areal sections on n different height levels, where n is between 3 and 16. In a preferred embodiment, the subwavelength gratings exhibit a z-shaped metal profile.
Also the subwavelength gratings can be combined with a diffraction pattern that splits the incident electromagnetic radiation spectrally. To spectrally broaden the resonances that occur, the subwavelength gratings can exhibit grating lines of a varying width.
In an advantageous development of the present invention, laterally different color impressions are produced through subwavelength gratings that exhibit a lateral variation in the grating profiles, especially a lateral variation in the profile depths. In this way, arbitrary colored images, for example screened color images that consist of a plurality of small and different colored pixel elements, can be introduced into the security elements.
In an advantageous embodiment, the security element includes, composed of a plurality of pixel elements, a colored image, the grating profiles being, in each case, constant within a pixel element, and in which the grating profiles of different colored pixel elements are differently developed in accordance with the color impression desired in each case. Alternatively, the color impression of a pixel element can also be produced through color mixing of sub-regions having different grating profiles. For example, three different types of sub-regions can be provided for the colors red, green and blue, and the color impression of each pixel element determined by the choice of the area percentages of the three sub-regions in accordance with the desired RGB value of the pixel.
The color image production through subwavelength gratings is suitable especially for obliquely metallically vapor-deposited dielectric gratings that display different colors in transmission and reflection, as explained below in greater detail. Here, due to the asymmetrical grating profile, an asymmetry of the color appearance is normally also observed at the viewing angle in transmission or in reflection. The lateral variation in the grating profile can especially consist in a lateral variation of the trench depth of the metalized dielectric grating. In addition to binary patterns, also obliquely vapor-deposited asymmetrical multilevel profiles having laterally different depths may be considered.
To produce subwavelength gratings having different profile depths, the following approach, for example, can be used: First, photoresist is applied to a grating substrate having a laterally constant trench depth, such that the trenches are completely filled. Then the substrate having the applied photoresist is impinged on with laser radiation of laterally differing intensities and the trenches partially exposed through removal of the exposed photoresist.
For the color production, as the underlying physical effect, especially polarization conversion through resonance excitation at gratings may be considered, which leads to a selective transmission or reflection when a subwavelength grating is arranged between two crossed polarizers.
The grating periods of the subwavelength gratings are preferably between 10 nm and 500 nm, preferably between 50 nm and 400 nm, and particularly preferably between 100 nm and 350 nm.
The subwavelength gratings can be formed by linear, one-dimensional gratings or also by two-dimensional cross-line gratings that are periodic in one or two spatial directions. In a further variant, the subwavelength gratings are formed by repeated one- or two-dimensional arrangement of metallic pattern elements, the pattern elements especially being formed in the shape of squares, rectangles, circular areas, ring patterns, strips or a combination of these elements or another arbitrary shape. As further shapes, especially spheres, rhombuses or rods, but also strongly asymmetrical shapes, such as open rings, may be considered. All cited arrangements can be periodic in one or two spatial directions.
In addition to one- or two-dimensional linear gratings, according to the present invention, also one- or two-dimensional curved gratings can be provided. In these curved gratings, the azimuth angle of the grating lines changes continually without abrupt jumps. Here, the azimuth angle indicates the local angle between the grating lines (more precisely a tangent to the grating lines) and a reference direction, so describes the local orientation of the grating lines in the plane.
The subwavelength gratings can be integrated in an interference layer system in order to modify or amplify their optical effect.
In all variants of the present invention, the feature region can be present in the form of patterns, characters or a code.
Due to the smallness of the metallic nanopatterns, these can particularly advantageously be used in security elements whose feature regions include micropatterns having a line width between about 1 μm and about 10 μm. Micro-optical moiré magnification arrangements, as are described in publications DE 10 2005 062 132 A1 and WO 2007/076952 A2, moiré-type micro-optical magnification arrangements, as are described in applications DE 10 2007 029 203.3 and PCT/EP2008/005173, and modulo magnification arrangements, as are described in application PCT/EP2008/005172, constitute examples of such security elements. All these micro-optical magnification arrangements include a motif image, having micropatterns, that reconstructs a specified target image when viewed with a suitably coordinated viewing grid. Here, as explained in greater detail in the above-mentioned publications and applications, it is possible to produce a plurality of visually attractive magnification and movement effects that lead to a high recognition value and a high counterfeit security of the security elements produced.
In an advantageous development of the present invention, for this, the micropatterns form a motif image that is subdivided into a plurality of cells, in each of which are arranged depicted regions of a specified target image. The lateral dimensions of the depicted regions are preferably between about 5 μm and about 50 μm, especially between about 10 μm and about 35 μm. In the first micro-optical moiré magnification arrangements mentioned above, the depicted regions of the cells of the motif image each constitute scaled-down images of the specified target image that fit completely within a cell. In the moiré-type micro-optical magnification arrangements, the depicted regions of multiple spaced-apart cells of the motif image constitute in each case, taken together, a scaled-down likeness of the target image, whose dimension is larger than one cell of the motif image. In the most general case, the magnification arrangement constitutes a modulo magnification arrangement in which the depicted regions of the cells of the motif image each constitute incomplete sections of the specified target image that are mapped by a modulo operation.
The security element preferably further exhibits a viewing grid composed of a plurality of viewing grid elements for reconstructing the specified target image when the motif image is viewed with the aid of the viewing grid. Here, the lateral dimensions of the viewing grid elements are advantageously between about 5 μm and about 50 μm, especially between about 10 μm and about 35 μm.
In the special case of a micro-optical moiré magnification arrangement, a motif image composed of a planar periodic or at least locally periodic arrangement of a plurality of micromotif elements is preferably applied as the micropattern. Here, the lateral dimensions of the micromotif elements are advantageously between about 5 μm and about 50 μm, preferably between about 10 μm and about 35 μm. In addition, the opposing side of the substrate is expediently provided with a planar periodic or at least locally periodic arrangement of a plurality of microfocusing elements for the moiré-magnified viewing of the micromotif elements of the motif image. In some embodiments, it is appropriate to arrange the microfocusing elements and the micromotif elements on the same side of the substrate. Also two-sided embodiments in which a micromotif element arrangement can be viewed through two opposing microfocusing element arrangements may be considered.
The present invention also includes a method for manufacturing a security element of the kind described, in which, in a feature region, the security element is provided with metallic nanopatterns in which volume or surface plasmons are excited and/or resonance effects are caused by the incident electromagnetic radiation.
Here, in an advantageous method variant, as metallic nanopatterns, metallic nanoparticles embedded in a carrier medium are applied to, especially imprinted on, a substrate.
If the metallic nanoparticles are magnetic, then they can be aligned and/or arranged by an external magnetic field after the application to the substrate. The nanoparticles are expediently immobilized after the alignment and/or arrangement by drying or curing the carrier medium.
In an advantageous development, the substrate is provided with a patterned surface having elevations and depressions, and metallic nanoparticles are introduced into the depressions of the patterned surface. For this, advantageously, a fluid carrier medium having the metallic nanoparticles can be applied to, for example imprinted on, the patterned surface, and the patterned surface then squeegeed or wiped such that the metallic nanoparticles are left only in the depressions of the patterned surface. Thereafter, the patterned surface having the nanoparticles introduced into the depressions is advantageously covered with a lacquer layer.
In another likewise advantageous method variant, as metallic nanopatterns, one or more subwavelength gratings having grating periods below the wavelength of visible light are applied to a substrate. For this, a relief pattern, for example, can be embossed in an embossing lacquer layer in the form of the desired subwavelength gratings, and a metalization applied to, especially vapor-deposited on, this relief pattern. The metalization is expediently deposited at a deposition angle Q that is between 0° and 90°, preferably between 30° and 80°. The metalized relief pattern is then advantageously covered with a further lacquer layer.
As the subwavelength gratings, also a repeated one- or two-dimensional arrangement of metallic pattern elements can be applied to, especially vapor-deposited on, the substrate, as described in greater detail below.
In a further advantageous manufacturing process, the nanopatterns are produced through laser irradiation of a thin metal layer. Here, the metal layer can be arranged on patterned or unpatterned regions of a substrate and either lie free or be embedded. The metal layer can be both contiguous and be contiguously bombarded with a laser, and be developed only in some regions, such that the laser irradiation leads to the formation of nanopatterns only in the metalized and illuminated regions. In a further embodiment, a contiguous metal layer can be vertically or obliquely illuminated with laser radiation, for example the radiation of a focused laser, only at predetermined sites such that nanopatterns are created only at the illuminated sites.
The present invention further includes a security paper for manufacturing value documents or the like, as well as a data carrier, especially a value document, such as a banknote, a passport, a certificate, an identification card or the like. According to the present invention, the security paper or the data carrier is furnished with a security element of the kind described. The security element can, especially if it is present on a transparent or translucent substrate, also be arranged in or over a window region or a through opening in the security paper or the data carrier.
Further exemplary embodiments and advantages of the present invention are described below with reference to the drawings. To improve clarity, a depiction to scale and proportion is dispensed with in the drawings.
Shown are:
The invention will now be explained using the example of security elements for banknotes. For this,
Both security elements exhibit, in a feature region, metallic nanopatterns in which, by incident visible light, volume or surface plasmons are excited or resonance effects are caused that produce novel color effects that, due to the smallness of the coloring nanopatterns in each case, are very difficult to counterfeit.
As already explained above, plasmons constitute the eigenmodes of collective oscillations of the free electrons relative to the ion cores in metals, which eigenmodes can be excited by incident electromagnetic radiation. At a certain wavelength, the freely movable charge carriers are excited to resonant oscillations, such that the light of this wavelength is preferably absorbed and scattered in all spatial directions. Radiation having wavelengths outside of the resonance range, in contrast, can pass largely undisturbed.
Due to this effect, the metallic nanopatterns according to the present invention appear, when looked through, having a color impression that results from the wavelengths of the uninfluenced, non-resonant portion of the incident light. When viewed in reflection, in which the scattered light dominates the visual appearance, the color impression of the nanopatterns is determined, in contrast, mainly by the resonant portion of the spectrum. Which wavelengths can excite the resonant plasma oscillations depends, in addition to the material of which the nanopatterns consist, also on the shape and size of the nanopatterns and the embedding medium.
The exemplary embodiment in
The nanoparticles 28 exhibit a diameter below the wavelength of visible light, preferably between 300 nm and 5 nm and especially between 200 nm and 10 nm. In a preferred variant of the present invention, the nanoparticles 28 are gold or silver particles. However, also other metals, such as copper, aluminum, nickel, chrome, tungsten, vanadium, palladium, platinum or alloys of these metals, display, even if to some extent in attenuated or modified form, color effects due to plasmon excitation, so that also these metals or metal alloys may be considered as material for the nanoparticles 28.
In addition to spherical nanoparticles 28, also differently formed particles, such as rotation ellipsoids, arbitrary polyhedra or also rod- or platelet-shaped particles can be used. Particles that deviate from the spherical shape additionally display, when they are oriented toward a preferred direction in space, effects that are dependent on the polarization direction of the incident light.
In addition to homogeneous metallic nanoparticles 28, also coated core-shell particles may be considered for the color production. These can exhibit both a metallic core having a dielectric or metallic shell and a dielectric core having a metallic casing. Silver particles having a TiO2 shell and polystyrene cores having a gold coating are examples of such embodiments. The number of combination possibilities here is almost unlimited, particularly since, in addition to the amorphous phase, the materials can also be present in crystalline or polycrystalline form.
In the simplest case, the transparent lacquer 26 in which the nanoparticles 28 are dissolved is contiguously applied to, for example imprinted on, the substrate 22, as shown in
In the exemplary embodiment in
When viewed in reflection 32, where the light scattered by the nanoparticles 28 dominates the color impression, the feature layer 24 thus appears green. In transmission 34, in contrast, the feature layer 24 appears in the subtractive complementary color, so having a red color impression.
Unlike with periodic diffraction patterns or interference layer systems, the color impression of the metallic nanoparticles is not dependent on the angle of incidence of the radiation and the viewing direction. Upon tilting, the security elements according to the present invention also do not run through the visible spectrum or sections thereof, but rather exhibit a substantially constant color impression. Since the color effects are caused by nanopatterns that are substantially smaller than the period of conventional diffraction gratings, they exhibit a particularly high counterfeit security, since such small patterns can hardly be manufactured with conventional methods, such as direct exposure or dot matrix methods.
Instead of being developed to be contiguous, the feature region of the security element 20 can also be designed in the form of patterns, characters or a code. It is also possible to provide, in different sub-regions of the feature region, different metallic nanopatterns, for example nanoparticles 28 composed of different materials and/or nanoparticles 28 of different shapes and sizes. In this way, different regions of the feature region can be colored differently.
Furthermore, the lacquer 26 provided with the coloring nanoparticles 28 can additionally include conventional color or effect pigments in order to modify the observable color effects. Also different kinds of metallic nanoparticles 28, for example having varying diameters, can be mixed with one another in order to produce a desired color effect in coaction.
In a further embodiment, measures can be taken to influence the spatial distribution of nanoparticles 28 that are initially dispersed homogeneously in a carrier medium, or the preferred direction non-spherical nanoparticles. This can happen, for example, in that the nanoparticles are furnished with a magnetic core, such that they can be concentrated at the intended locations of the feature region with the aid of spatially varying magnetic fields. Here, the nanoparticles 28 are initially still movable in the carrier medium 26. Only after they were positioned and/or aligned with the aid of the magnetic fields are they immobilized in that the binder of the carrier medium 26 is cured, for example by drying or irradiation with UV light, or the carrier medium 26 or at least the solvent included therein is evaporated by the addition of heat.
Functionalized surfaces of nanoparticles offer additional possibilities to influence the arrangement of the nanoparticles. For example, through a suitable functionalization of the surface, it can be achieved that the particles arrange themselves at a certain spacing and/or in a defined grating. Furthermore, a clustering of the nanoparticles can be prevented through a suitably chosen functionalization.
Also a functionalization of the substrate surface can serve the arrangement and periodic alignment of the nanoparticles. Through a functionalization of the substrate surface and, if applicable, also the surface of the nanoparticles, said nanoparticles can be systematically deposited on predefined regions of the substrate. In this way, it is possible, for example, to arrange the nanoparticles on grating lines in order to influence, for example to intensify, the diffraction property of the grating.
Alternatively, also nanoparticles 28 that are unmagnetic per se can be coupled through functional coatings to magnetic carrier particles that then, together with the coloring nanoparticles 28 are systematically arranged and/or aligned by external magnetic fields.
According to a preferred variant of the present invention, the distribution of the nanoparticles 28 is systematically influenced by a patterning of the surface to which they are applied. For example, as shown in the exemplary embodiment in
In order to prevent the nanoparticles 48 from falling out of the depressions 44 during the further processing, the structure can be covered with a further lacquer layer that is not depicted in the figures. If the lacquer used for covering flows around the nanoparticles 48, then also the refractive index of the medium embedding the particles can be defined in this way. However, it is currently preferred that the nanoparticles 48 remain embedded in the original carrier medium 46 that, together with the nanoparticles 48, remains in the depressions 44 when the surface is squeegeed.
In the exemplary embodiment shown in
According to an advantageous manufacturing variant, also the micro intaglio printing technique described in international patent application PCT/EP2007/005200 can be used, which combines the advantages of printing and embossing technologies. Summarized briefly, in the micro intaglio printing technique, a die form is provided whose surface exhibits an arrangement of elevations and depressions in the form of a desired micropattern. The depressions in the form are filled with a curable colored or colorless lacquer that contains the nanoparticles, and the substrate to be printed on is pretreated for a good anchoring of the lacquer. Then the surface of the die form is brought into contact with the substrate, and the lacquer that, in the depressions in the die form, is in contact with the substrate is cured and, in the process, joined with the substrate. Thereafter, the surface of the die form is removed from the support again such that the cured lacquer that is joined with the support and having the nanoparticles is pulled out of the depressions in the die form. For a more detailed description of the micro intaglio method and the associated advantages, reference is made to the cited patent application PCT/EP2007/005200, the disclosure of which is incorporated in the present application by reference.
In the security elements described above, the visual impression can not only be produced by the effects of the plasmon excitation in the nanoparticles 48, but can also be influenced by diffraction effects on the patterns that are specified by the elevations 42 and depressions 44. In the case of periodically arranged linear trenches, in addition to the described plasmon effects, for example, a spectral splitting of the light that is typical for diffraction on a linear grating can appear. These diffraction effects can be systematically integrated in the design of the security element. If such additional, strongly color-producing effects are undesired in other embodiments, then the elevations and depressions 42, 44 can also be arranged irregularly and diffraction-based color appearances largely suppressed.
For illustration,
In the top view of the feature region 62 in
In some embodiments, the semitransparent absorber layer 76 can also be dispensed with. If the security element 70 is to be used in transmission, so for example in the see-through window of a banknote, then the lower metal layer 74 is expediently designed to be semitransparent.
It is understood that, also in the exemplary embodiments in
The manufacture of the metallic nanoparticles themselves can occur through physical or chemical methods known to the person of skill in the art. Laser ablation is an example of a physical method.
Instead of resorting to prefabricated nanoparticles that are dissolved in suitable media and applied to a desired substrate through, for example, printing, according to a further aspect of the present invention, also one or more subwavelength gratings can be applied directly to the substrate of the security element. On the one hand, such periodic nanopatterns permit more intense color effects than the previously described metallic nanoparticles, and on the other hand, the multitude of degrees of freedom at manufacture further increases the counterfeit security of such security elements.
In subwavelength gratings, exceptional intensity changes can occur in the transmission or in the reflection if the incident light leads to resonances in the interstices or in the cavities in the grating pattern. Here, in transmission gratings, one can observe a strong intensity shift between reflection and transmission for certain wavelength ranges. These so-called cavity resonances likewise lead to an increased absorption of the light. It is worth mentioning that this effect can also induce an exceptional transmission increase.
Also the so-called Wood's anomalies influence, independently of the polarization of the incident light, the transmission or reflection spectra of gratings in the zeroth diffraction order. A Wood's anomaly is associated with the creation of a new diffraction order, that is, it occurs when the angle of reflection is 90°. The spectral positions of the Wood's anomalies can thus be derived from the grating equation. They result for wavelengths λ=(p/m) (1±sin α), where p represents the grating period, α the angle of incidence and m the diffraction order. When a diffraction order disappears, its intensity must be redistributed to the remaining diffraction orders, which also leads to a spectral intensity change in the zeroth diffraction order. Finally, an increase in the transmission, with an attendant reduction in the reflection, was observed in wire gratings for wavelengths of the Wood's anomalies under TE polarization (e-vector parallel to the grating pattern). For increasingly larger wavelengths, the transmission is reduced and finally, in the limiting case, approaches zero.
For illustration, first, patterns are described that exhibit a periodicity only in one dimension.
In this way, a metallic binary pattern 86 that is embedded in the lacquer layers 84, 88 and that includes exclusively planar metallic areal sections on only two different height levels (metallic bi-grating) results. The metallic areal sections can also be arranged on more than two height levels, especially on n=3 to n=16 different height levels, and in this way form a more general multilevel pattern.
If the deposition angle Q of the metal layer 90 deviates from 90°, a subwavelength grating having a z-shaped metal profile is created, as illustrated in
The transmission or reflection spectra of such subwavelength gratings can be calculated, for example, with the aid of electromagnetic diffraction theories. To be able to estimate the perceived coloring of these gratings, the spectrum calculated for the visible wavelength range is folded with the spectrum of the standard lamp D65 and the sensitivity curves of the human eye. This yields the parameters X, Y and Z that reflect the color values red, green and blue.
The special case of vertical vapor deposition shown in
A strong coloring of a nanopattern results when one of the color values X, Y, Z is dominant with respect to the other color values, or when the color values strongly differ from one another. As can be seen from the curve shapes 100, 102 and 104 in
For the color perception, it is further desirable that the reflection of an object is at least 20% so that the color spectrum reflected at the object stands out from the reflected light of the surrounding medium. The transmission, in contrast, can be lower for the color perception, since usually only the transmitted light of the object is observed and the scattered light of the surroundings is covered. For the light intensity of the grating described above, a reflection of 30% to 60% and a transmission between 5% and 45% is obtained for a deposition angle Q in the range between 30° and 90°. Here, for more oblique deposition angles, the transmission increases while the reflection decreases.
In addition to the described effects, for the subwavelength gratings according to the present invention, the color effect changes when viewed in polarized light. This also distinguishes the inventive coloring feature regions of colored surfaces that were produced with conventional means. For example, for subwavelength gratings having the above-mentioned grating parameters, especially the intensity of the color value Z (blue) changes with the polarization of the incident light, the differences between TE polarization (e-vector of the incident light parallel to the grating lines) and TM polarization (e-vector of the incident light vertical to the grating lines) being particularly large at a deposition angle in the region of Q=45°.
Here, due to the asymmetric grating profile, also an asymmetry of the color appearance in the viewing angle is observed in transmission or in reflection. Through systematic lateral variation in the grating profiles, especially the profile depths, it is thus possible to produce laterally different color impressions within the security element and thus also color images, as described above in detail.
In further exemplary embodiments of the present invention, the described subwavelength gratings can be combined with a diffraction pattern that spectrally splits incident electromagnetic radiation. For illustration,
If locally varying widths of the metallic grating lines are used, for example a modulation of the grating line width in the form of a beat or a statistical variation in the grating line widths, then the plasmon resonances can be spectrally broadened. In this way, a broader range of the visible light spectrum can be influenced in its intensity than would be the case through a strictly periodic grating.
In generalization of the one-dimensional subwavelength gratings described so far, also two-dimensional cross-line gratings can be used that are arranged periodically or also statistically in one or two spatial directions.
Due to the rectangular design of the cross-line grating 122, the period lengths in the x-direction and the y-direction, px and py, are, in general, different. For different period lengths px, py, the cross-line grating 122 produces a different color impression in polarized light, depending on whether the light is polarized vertically or horizontally. When viewed with unpolarized light, the viewer perceives a mixed color. If, in contrast, the period lengths px and py are identical, then, when viewed with unpolarized light, the cross-line gratings look just as if one were viewing it with vertically or horizontally polarized light.
The one- or two-dimensional subwavelength gratings can also be formed by a repeated arrangement of metallic pattern elements, with, in addition to quadratic or rectangular elements, especially also circular, elliptical, ring-shaped or arbitrarily formed elements being able to be considered.
In the top view 134 in
In general, the elements of arbitrary shape can be distributed statistically or stochastically on the surface that is to appear colored.
It is understood that the variants described for the one-dimensional subwavelength gratings, especially the use of Wood's anomalies and the combination of the subwavelength gratings with diffraction gratings, can also be used for two-dimensional cross-line gratings and the one- or two-dimensional pattern element arrangements.
The described subwavelength gratings can also be integrated in an interference layer system in order to modify or amplify their optical effect. An exemplary layer system is shown in the cross section in
Thereafter, a layer 146 having a high refractive index, preferably ZnS or TiO2, is applied, for example likewise through vapor deposition. Whether or how clearly the embossing pattern is still reflected at the surface of this high-index layer 146 depends on the circumstances under which the layer was applied. The most important parameter in this regard is, of course, the layer thickness. The interference layer system is completed by application of a further layer 148 of a transparent material having a lower refractive index, for example protective lacquer with n=1.5. The optical effect of the high-index dielectric layer 146 is substantially determined by its thickness and the difference between the refractive index and the surroundings.
The high resolution required for the described subwavelength gratings may be achieved, for example, with the aid of electron beam lithography systems, with even the smallest particles having a lateral dimension of some 10 nm still being able to be produced having individual contours. Here, PMMA is typically used as the resist. The origination by means of electron beam lithography is followed by galvanic casting and the manufacture of embossing tools with whose aid the nanopatterns can thereafter be replicated by embossing in UV-curing lacquer or a thermoplastically moldable plastic on foil webs. The metallic nanopatterns are obtained in the subsequent step through vapor deposition or sputtering with the corresponding material in the desired layer thickness, taking note that the metal layer thickness should normally be smaller than the embossing depth. Gold, silver, copper and aluminum are preferably used as the metals.
A particular advantage of the metallic nanopatterns according to the present invention consists in that, even in small micropatterns having dimensions of a few micrometers, they can be arranged in a sufficient number of periods or quasiperiods. Typical examples of such micropatterns are letters and symbols that form the micromotif images of a moiré magnification arrangement. The operating principle and advantageous arrangements for such moiré magnification arrangements are described in publications DE 10 2005 062 132 A1 and WO 2007/076952 A2, the disclosure of which is incorporated in the present application by reference.
If such micropatterns are filled with nanopatterns according to the present invention, they can be lent a coloring that is very difficult to achieve, or is simply unachievable, in another manner, especially with multiple colors in a very small space.
In the variant of the present invention shown in
The color production or blackening is accomplished by the excitation of plasmons in the respective nanopatterns 152, 156, 158, as already described above. In the case of the filling with the line grating 156, whose period should be significantly smaller than the wavelength of visible light, in addition to the color effect, also a polarizing effect will be observed. Which color, in detail, is created depends on the composition of the nanopatterns and the type of dielectric embedding, as already explained in detail. The deterministic patterns 156, 158 in
In the profile shapes created, the areal sections provided with nanopatterns can be located on the plane of the vellum region or be offset downward or upward compared with this plane. Typical embossing depths are in the range between 10 nm and 500 nm for the nanopatterns and up to a maximum of 10 μm for the micropatterns.
Furthermore, the regions that are offset upward or downward and that define the areas of the micromotif elements 150 can also exhibit curved profiles.
In the depictions in
In addition to the embodiments described so far, the nanopatterns can also change within a micropattern, for example continually, abruptly or statistically. The same applies for the nanopattern filling of the vellum region: it, too, need not necessarily be homogeneous, as shown in the exemplary embodiments in
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10 2007 061 979 | Dec 2007 | DE | national |
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PCT/EP2008/010747 | 12/17/2008 | WO | 00 | 6/18/2010 |
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WO2009/083151 | 7/9/2009 | WO | A |
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