CN115083256A - Anti-counterfeit label, composite optical structure, preparation method and application thereof - Google Patents
Anti-counterfeit label, composite optical structure, preparation method and application thereof Download PDFInfo
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- CN115083256A CN115083256A CN202210193877.1A CN202210193877A CN115083256A CN 115083256 A CN115083256 A CN 115083256A CN 202210193877 A CN202210193877 A CN 202210193877A CN 115083256 A CN115083256 A CN 115083256A
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Abstract
The invention relates to the field of optical anti-counterfeiting, and discloses a composite optical structure with angular responsiveness, an anti-counterfeiting label, and a preparation method and application thereof. The composite optical structure of the present invention comprises: the photonic crystal structure includes a substrate, a photonic crystal layer formed on the substrate, and a grating layer formed on the photonic crystal layer. The anti-counterfeiting label comprising the composite optical structure disclosed by the invention has the advantages that the displayed color is not easy to be imitated by common pigment or dye, and the anti-counterfeiting effect is good.
Description
Technical Field
The invention relates to the field of optical anti-counterfeiting, in particular to a composite optical structure with angular responsiveness, an anti-counterfeiting label, and a preparation method and application thereof.
Background
Structural colors are widely present in nature and in life. Different from dyes, the structural color is generated by the phenomena of interference, scattering, diffraction and the like due to the interaction of light and a substance micro-nano structure, so that the structural color depends on the structure of the substance, is more stable and environment-friendly compared with the dyes, and cannot fade as long as the structure is not damaged.
Photonic crystals are a class of materials whose dielectric constants vary periodically on an optical scale and whose fundamental property is to have a photonic band gap. When the bandgap of the photonic crystal is in the visible region, it means that light of a particular frequency is reflected by the surface and exhibits a color specific to that band. The color is the structural color of the photonic crystal, has the advantages of high saturation, high brightness, fastness, dynamic regulation and the like which are not possessed by other chemical colors, and has wide application in the anti-counterfeiting field.
At present, anti-counterfeiting by utilizing responsive photonic crystals is the most common anti-counterfeiting mode. The photonic band gap of a responsive photonic crystal can respond to changes in the external environment. Materials can exhibit a change in color on a macroscopic scale when the photonic band gap falls within the visible range. The color moisture sensitive photonic crystal hydrogel was prepared by photo-polymerizing a P (St-MMA-AA) photonic crystal template impregnated with an acrylamide (AAm) solution as reported in document j.mater.chem.2008,18,1116-1122. When the humidity is increased, the volume of the polyacrylamide expands, so that the micro-nano structure (lattice constant) of the photonic crystal is changed, and the structural color of the photonic crystal hydrogel is changed accordingly. The document adv.mater.2009,21, 4259-. The photonic crystal paper can be used for writing characters or patterns on the paper by using a saline solution as ink. The structure (lattice constant) of the photonic crystal in the saline solution written region changes and thus may exhibit a different structural color from the unwritten region. The photonic crystal paper can be applied to the anti-counterfeiting field. However, the above-mentioned anti-counterfeiting method using a responsive photonic crystal usually causes damage to the structure of the photonic crystal and cannot be used for a long time.
The anti-counterfeiting method is simple and convenient and does not damage the photonic crystal structure by utilizing the angle resolution characteristic of the photonic crystal structure color. For example, CN105693903A discloses a method for preparing an anti-counterfeiting pattern based on photonic crystal structural color, and achieves an anti-counterfeiting effect by means of the angle resolution characteristic of the photonic crystal structural color. The chem.mater.2013,25, 2684-. The subject group utilizes a high molecular monomer emulsion containing silicon dioxide nano particles to prepare a patterned photonic crystal anti-counterfeiting label by technologies such as photoetching. The photonic crystal pattern has a bright structural color and an angle resolution characteristic. When the viewing angle is changed from 10 degrees to 55 degrees, the color of the label will change from green to blue to purple. However, the structural color materials for anti-counterfeiting by using the angle resolution characteristic are generally composed of a single optical structure, so that the optical change process of the anti-counterfeiting label is single, the color is only changed from long wavelength to short wavelength or from short wavelength to long wavelength, the anti-counterfeiting security grade is low, and the anti-counterfeiting label is easy to imitate.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a novel composite optical structure with angular responsiveness, a preparation method thereof and application thereof in the field of anti-counterfeiting.
To achieve the above object, an aspect of the present invention provides a composite optical structure, wherein the composite optical structure includes: the photonic crystal structure includes a substrate, a photonic crystal layer formed on the substrate, and a grating layer formed on the photonic crystal layer.
Preferably, the photonic crystal layer includes one or more of a one-dimensional photonic crystal, a two-dimensional photonic crystal, and a three-dimensional photonic crystal.
Preferably, the photon forbidden band range of the photonic crystal is 300-1500 nm; more preferably, the photon forbidden band range of the photonic crystal is 380-780 nm.
Preferably, the photonic crystal layer is a one-dimensional photonic crystal layer, a two-dimensional photonic crystal layer, or a three-dimensional photonic crystal layer.
Preferably, the one-dimensional photonic crystal layer is prepared by one or more methods selected from an alternating coating method, a spin coating method, a spray coating method, a pulling method, an LB film technology, and a layer-by-layer stacking technology.
Preferably, the two-dimensional photonic crystal layer is prepared by one or more of a self-assembly method, an etching method, and a multi-beam interference method.
Preferably, the three-dimensional photonic crystal layer is prepared by one or more methods selected from a self-assembly method, a layer-by-layer stacking technique, a holographic lithography method and a sacrificial template method.
Preferably, the grating layer comprises a one-dimensional grating and/or a two-dimensional grating.
Preferably, the groove shape of the grating is sinusoidal, rectangular or sawtooth.
Preferably, the grating layer is in the form of a film.
Preferably, the grating layer is prepared by one or more methods selected from holographic interferometry, electron beam exposure, focused ion beam processing, optical lithography, two-beam interferometry, laser direct writing, and nanoimprint.
Preferably, the material of the grating layer is an organic material and/or an inorganic material; more preferably, the material of the grating layer is PMMA, PDMS, PS, PVA, Ag, Al and Al 2 O 3 One or more of;
preferably, the thickness of the grating layer is 200nm-20 μm, more preferably 200nm-10 μm.
Preferably, the period of the grating is 400nm-20 μm, more preferably 700-1500 nm.
According to a second aspect of the present invention, there is provided a method of making a composite optical structure, wherein the method comprises the steps of,
1) a step of forming a photonic crystal layer on a substrate;
2) and forming a grating layer on the photonic crystal layer.
According to a third aspect of the invention there is provided a security label comprising a composite optical structure according to the invention.
According to a fourth aspect of the invention, there is provided the use of a composite optical structure according to the invention in the field of anti-counterfeiting.
Through the technical scheme, the beneficial effects of the invention comprise:
1) the invention provides a composite optical structure with angular response characteristic, and the anti-counterfeiting label comprising the composite optical structure has the advantages that the displayed color is not easy to be imitated by common pigment or dye, and the anti-counterfeiting label has good anti-counterfeiting effect.
2) According to the invention, different optical phenomena can be observed by adjusting the observation angle, rather than only single color change, the anti-counterfeiting safety grade is high, and the anti-counterfeiting process cannot damage the optical structure.
3) The preparation method of the composite optical structure is simple and environment-friendly, and has short preparation period and low cost.
Drawings
FIG. 1 is a scanning electron micrograph of a photonic crystal prepared by a vertical deposition method of monodisperse poly (styrene-methyl methacrylate-acrylic acid) latex particles of example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a cross-section of a photonic crystal prepared by a vertical deposition method of monodisperse poly (styrene-methyl methacrylate-acrylic acid) latex particles of example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of a grating structure prepared by a nanoimprint method according to example 1 of the present invention;
FIG. 4 is a schematic cross-sectional view of the anti-counterfeit mark with a composite optical structure prepared in example 1 of the present invention;
FIG. 5 is a schematic view of the color of the anti-counterfeit mark with composite optical structure prepared in example 1 of the present invention at different angles;
FIG. 6 is a schematic view of colors observed at different angles of the composite optical structure anti-counterfeiting mark prepared in example 6 of the present invention;
fig. 7 is a schematic view of colors observed at different placing angles of the composite optical structure anti-counterfeiting mark prepared in example 7 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
One aspect of the present invention provides a composite optical structure, wherein the composite optical structure comprises: the photonic crystal structure includes a substrate, a photonic crystal layer formed on the substrate, and a grating layer formed on the photonic crystal layer.
According to the present invention, the composite optical structure may be a material that can exhibit two or more of a photonic crystal structure color, a mixed color of the photonic crystal structure color and the grating structure color, and a grating structure color at different angles.
According to the invention, the substrate may be a rigid substrate or a flexible substrate; preferably, the substrate is any one of Si, glass (glass slide), a PET film, a PDMS film, and an Al film. In the present invention, the size of the substrate is not limited, for example, it can be 1cm × 1cm silicon wafer, 5cm × 2.5cm PET film, 3cm × 1cm glass slide, etc., and the substrate with corresponding size can be selected according to the specific size requirement of the prepared composite optical structure, and generally, the size of the prepared composite optical structure is smaller than that of the substrate.
According to the invention, the photonic crystal refers to an artificial periodic dielectric structure with photonic band gap characteristics, and comprises a one-dimensional photonic crystal, a two-dimensional photonic crystal and a three-dimensional photonic crystal.
In the present invention, preferably, the photonic crystal layer includes one or more of a one-dimensional photonic crystal, a two-dimensional photonic crystal, and a three-dimensional photonic crystal.
More preferably, the photonic crystal layer is a one-dimensional photonic crystal layer, a two-dimensional photonic crystal layer, or a three-dimensional photonic crystal layer.
The one-dimensional photonic crystal layer is a layer formed by one-dimensional photonic crystals; the two-dimensional photonic crystal layer is a layer formed of a two-dimensional photonic crystal; the three-dimensional photonic crystal layer refers to a layer formed of a three-dimensional photonic crystal.
According to the invention, the one-dimensional photonic crystal is a photonic crystal with dielectric constants arranged periodically in one direction, and mainly comprises a multilayer film formed by periodically arranging different media. The preparation method comprises an alternating coating method, a spin-coating method, a spraying method, a pulling method, an LB film technology, a layer-by-layer stacking technology and the like.
According to the invention, the two-dimensional photonic crystal is a photonic crystal with dielectric constants arranged periodically in two directions, and mainly comprises a grating structure, a two-dimensional lattice structure and the like. The preparation method comprises a self-assembly method, an etching method, a multi-beam interference method and the like.
According to the invention, the three-dimensional photonic crystal is a photonic crystal with dielectric constants arranged periodically in three directions, and mainly comprises a diamond structure, an opal structure, an inverse opal structure photonic crystal and the like. The preparation method comprises a self-assembly method, a layer-by-layer stacking technology, a holographic lithography method, a sacrificial template method and the like. Such as three-dimensional ordered array structures prepared from monodisperse inorganic or organic particles (also called colloidal particles) with diameters in the micrometer or submicron range, self-assembly methods, and macroporous materials with three-dimensional ordered structures prepared using colloidal crystals as templates.
According to the present invention, the colloidal particles may be one or more of organic nanoparticles, inorganic nanoparticles, and organic-inorganic composite nanoparticles; preferably, the colloidal nanoparticles are one or more of polymer nanoparticles, polystyrene, poly (styrene-methyl methacrylate-acrylic acid), polymethyl methacrylate, silica, carbon spheres, cuprous oxide, copper oxide, cadmium sulfide, lead sulfide, titanium dioxide, zinc sulfide, and zinc oxide.
According to the invention, the structure of the colloidal nanoparticles is an ordered stacking structure or a disordered stacking structure, wherein the ordered stacking structure is any one of a hexagonal close stacking structure, a cubic stacking structure and a non-close stacking structure, and the disordered stacking structure comprises a short-range ordered long-range disordered stacking structure; in the present invention, the short-range ordered long-range unordered stacked structure is understood as "short-range ordered" which is "unordered" in the whole stacked structure, that is, the "short-range ordered" is limited to a specific small range and is "ordered".
According to the invention, preferably, the photon forbidden band range of the photonic crystal is 300-1500 nm; more preferably, the photon forbidden band range of the photonic crystal is 380-780 nm.
According to the invention, a grating is an optical element consisting of a large number of parallel slits of equal width and equal spacing. The grating includes a one-dimensional grating and a two-dimensional grating. A one-dimensional grating is a grating having a periodic structure in one direction. A two-dimensional grating is a grating having a periodic structure in two directions.
According to the present invention, the period of the grating is preferably 400nm-20 μm, more preferably 700-1500 nm.
In the present invention, the grating layer may comprise a grating of one or more grating parameters.
According to the invention, the grating parameters include grating direction, period, depth, duty cycle.
Preferably, the grating layer comprises a one-dimensional grating and/or a two-dimensional grating.
According to the invention, the groove shape of the grating is preferably sinusoidal, rectangular, sawtooth-shaped, etc.
According to the present invention, preferably, the grating layer is film-shaped.
According to the present invention, preferably, the grating layer may be prepared by one or more methods selected from a holographic interference method, an electron beam exposure method, a focused ion beam processing method, an optical etching method, a two-beam interference method, a laser direct writing method and a nano-imprinting method; preferably, the grating layer is prepared by a nano-imprinting method.
According to the present invention, preferably, the material of the grating is an organic material and/or an inorganic material; more preferably, the grating material is PMMA (polymethylmethacrylate), PDMS (polydimethylsiloxane), PS (polystyrene), PVA (polyvinyl alcohol), Ag, Al and Al 2 O 3 One or more of (a).
According to the present invention, preferably, the thickness of the grating layer is 200nm to 20 μm, more preferably 200nm to 10 μm.
According to the invention, the grating layer may consist of one layer of material or of several layers of material.
According to the invention, the multilayer generally comprises two or three layers.
According to a second aspect of the present invention, there is provided a method of making a composite optical structure, wherein the method comprises the steps of,
1) a step of forming a photonic crystal layer on a substrate;
2) and forming a grating layer on the photonic crystal layer.
The method according to the present invention, which is obtained by preparing a photonic crystal layer on a substrate and then preparing a grating layer on the photonic crystal thin film, is as described above for the method for preparing a photonic crystal layer on a substrate and for preparing a grating layer on the photonic crystal layer, and will not be described again here.
According to a third aspect of the invention there is provided a security label comprising a composite optical structure according to the invention.
According to a fourth aspect of the invention, there is provided the use of a composite optical structure according to the invention in the field of anti-counterfeiting.
According to the invention, under the illumination condition, the photonic crystal layer and the grating layer can generate interaction with incident light to generate structural color, but because the photonic crystal layer and the grating layer generate structural color within different angle ranges, various color changes can be generated along with the change of the pitch angle during observation. The color change process comprises two or more color changes of the structural color of the photonic crystal, the mixed color of the structural color of the photonic crystal and the structural color of the grating.
Further, if the grating layer includes gratings with two or more grating directions, color change and pattern conversion can be achieved by rotating the grating in a plane.
Examples
In the following examples, the nanoparticles, chemicals or chemicals involved are commercially available, for example, PDMS from Dow Corning (Sylgard 184) and absolute ethanol from Kancoded technologies, Inc. of Tianjin.
In the following examples, the test methods involved are as follows: the structures of the photonic crystal and the grating were characterized by a scanning electron microscope (S-4800, hitachi, japan), and the scattering spectra of the composite optical structure were characterized by a macroscopic angle-resolved spectrometer (R1, shanghai yun science instruments ltd).
Example 1
This example illustrates a composite optical security label made in accordance with the present invention.
(1) Fully ultrasonically treating 0.1 mass percent of monodisperse poly (styrene-methyl methacrylate-acrylic acid) globule solution with the particle size of 210nm to uniformly disperse the poly (styrene-methyl methacrylate-acrylic acid) globule solution;
(2) cutting a 4cm multiplied by 3cm glass sheet, cleaning and carrying out hydrophilic treatment, vertically placing the glass sheet into the mixed solution, and assembling the monodisperse colloidal nanoparticles on the glass sheet substrate by using the capillary force of a meniscus of water formed on the surface of the glass sheet under the conditions that the temperature is 60 ℃ and the relative humidity is 60%;
(3) the glass wafer with the photonic crystal assembled thereon was placed in an oven at 80 ℃ and annealed for 1 hour to firmly bond the pellets to the glass wafer substrate, thereby forming a photonic crystal layer on the substrate, the photonic crystal layer having a thickness of about 9 μm. The photonic band gap position of the photonic crystal at 0 deg. incidence in this embodiment is about 519 nm.
(4) Separating an upper layer and a lower layer of the DVD disc, flushing the lower layer with ethanol, drying by using nitrogen, and mixing a component A (precursor) and a component B (curing agent) of PDMS according to a weight ratio of 10: 1 (PDMS, available from Dow Corning company as Sylgard 184), and then placed in a centrifuge at 3000r/min for 5min to remove bubbles generated during the mixing process. And casting the prepared PDMS on the surface of the DVD optical disk template, putting the sample in a vacuum drier, vacuumizing for 30min, taking out the sample, and putting the sample in an oven at 80 ℃ for heating for 2 h. After cooling to room temperature, the PDMS is slightly peeled off from the DVD optical disk template, and a PDMS soft template with the thickness of about 3mm can be obtained.
(5) Cutting the soft template obtained in the step (4) into a proper size, putting the soft template into a vacuum drier, dropwise adding a proper amount of fluorosilane into the soft template, vacuumizing the soft template for 20min, putting the soft template into an oven with the temperature of 80 ℃, heating the soft template for 2h, and performing hydrophobic treatment.
(6) Transferring 200 mu L of prepared PDMS by using a liquid transfer gun, spin-coating the transferred PDMS on the photonic crystal layer in the step (3) by using a KW-4A type spin coater, and keeping the transferred PDMS at a low speed (500r/min) for 5 s; keeping the temperature at a high speed (5000r/min) for 30s, placing the hydrophobic PDMS soft template in the step (5) on the PDMS layer after the spin coating is finished, placing the PDMS soft template in a vacuum drier, vacuumizing for 2min, taking out the sample, and placing the sample in an oven at 80 ℃ for heating for 1 h. And taking out the sample, slightly stripping the PDMS soft template to obtain a structure for forming the grating layer on the photonic crystal layer, and thus obtaining the photonic crystal and grating composite optical structure anti-counterfeit label. Wherein, the thickness of the grating layer is about 6 μm, the period of the grating is 75nm, and the depth of the grating structure is about 100 nm.
Fig. 1 is a scanning electron micrograph of a photonic crystal prepared by a vertical deposition method from monodisperse poly (styrene-methyl methacrylate-acrylic acid) latex particles of example 1, and it can be seen from fig. 1 that colloidal globules are closely arranged to form a face-centered cubic packing structure.
Fig. 2 is a scanning electron micrograph of a cross section of a photonic crystal prepared by a vertical deposition method from monodisperse poly (styrene-methyl methacrylate-acrylic acid) latex particles in example 1, and it can be seen from fig. 2 that colloidal globules are closely packed to form a three-dimensional photonic crystal structure.
Fig. 3 is an SEM image of the grating obtained in example 1, and it can be seen from fig. 3 that a one-dimensional grating structure having a period of 750nm was successfully prepared by nanoimprinting.
Fig. 4 is a schematic diagram of the composite optical structure in embodiment 1, and as shown in fig. 4, the composite optical structure is a composite optical structure of a photonic crystal and a grating, the lower layer is a substrate, the middle layer is a photonic crystal layer having a three-dimensional photonic crystal structure, and the upper layer is a grating layer having a grating structure.
Fig. 5 is a schematic view of colors observed at different angles of the anti-counterfeit label with a composite optical structure prepared in example 1, wherein it can be seen that the anti-counterfeit mark has different colors at different angles, for example, under the condition that the angle is changed from 0 to 90 degrees. Wherein, under the conditions that the incident angle of the light source is 0 DEG and the variation range of the observation angle is 0-10 DEG, the structural color and the green color of the photonic crystal in the prepared anti-counterfeiting label with the composite optical structure are observed, such as a picture marked with '1' in figure 5; under the conditions that the incident angle of a light source is 0 degrees and the angle change range is 30-90 degrees, the structural color of the grating in the prepared composite optical structure anti-counterfeiting label is observed to change from purple to red. If the angle variation range is 37-40 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be blue, such as a picture marked with '2' in figure 5; under the condition that the angle variation range is 41-50 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be green, such as a picture marked with '3' in figure 5; under the condition that the angle variation range is 56-90 degrees, the prepared anti-counterfeiting label with the composite optical structure is observed to be red, such as a picture marked with '4' in figure 5. Thus, anti-counterfeiting can be achieved by changing the viewing angle and thus the observed color.
Example 2
This example illustrates a composite optical structure security label made in accordance with the present invention.
(1) 5 wt% of polystyrene microsphere emulsion with the particle size of 600nm is prepared according to the following emulsion: water: absolute ethanol ═ 1: 1: 2, preparing the mixed solution, and carrying out ultrasonic treatment for 10 minutes to uniformly disperse the mixed solution.
(2) Cutting a 2cm multiplied by 2cm aluminizer, cleaning and carrying out hydrophilic treatment, placing the aluminizer in a glass culture dish, and pouring a proper amount of ultrapure water to ensure that the liquid level is higher than the surface of the substrate and is tangent to the silicon wafer; sucking a proper amount of polystyrene pellet mixed solution by using a liquid transfer gun, dropwise adding the mixed solution on a silicon wafer, driving the polystyrene pellets to diffuse on the liquid surface and assemble by quickly volatilizing ethanol in the mixed solution, sucking the proper amount of mixed solution again by using the liquid transfer gun after the solution is completely diffused, dropwise adding the mixed solution on the liquid surface, and repeating for multiple times to obtain a regularly assembled pellet array; when the whole liquid surface is fully paved with the small balls, a plurality of drops of sodium dodecyl sulfate solution are dripped on the edge of the glass culture dish, so that the small balls are arranged more tightly; sucking out excessive water with a suction pipe, standing for several hours, and transferring the assembled small ball array to an aluminized film substrate.
(3) The glass petri dish was placed in an oven at 80 ℃ and annealed for 1 hour to firmly bond the pellet to the aluminum-plated film substrate, thereby forming a photonic crystal layer on the substrate, the thickness of the photonic crystal layer being about 600 nm. In this embodiment, when the incident angle of 25 ° changes from 26 ° to 60 °, the position of the photon forbidden band changes from 459nm to 679 nm.
(4) Separating an upper layer and a lower layer of the DVD disc, flushing the lower layer with ethanol, drying by using nitrogen, and mixing the component A and the component B of PDMS according to a weight ratio of 10: 1, uniformly mixing and fully stirring, and then putting the mixture into a centrifuge to centrifuge for 5min at a speed of 3000r/min so as to remove bubbles generated in the mixing process. And casting the prepared PDMS on the surface of the DVD optical disk template, putting the sample in a vacuum drier, vacuumizing for 30min, taking out the sample, and putting the sample in an oven at 80 ℃ for heating for 2 h. After cooling to room temperature, the PDMS is slightly peeled off from the DVD optical disk template, and the PDMS soft template can be obtained.
(5) Cutting the soft template obtained in the step (4) into a proper size, putting the soft template into a vacuum drier, dropwise adding a proper amount of fluorosilane into the soft template, vacuumizing the soft template for 20min, putting the soft template into an oven with the temperature of 80 ℃, heating the soft template for 2h, and performing hydrophobic treatment.
(6) Transferring 200 mu L of prepared PDMS by using a liquid transfer gun, spin-coating the transferred PDMS on the photonic crystal layer in the step (3) by using a KW-4A type spin coater, and keeping the transferred PDMS at a low speed (500r/min) for 5 s; keeping the temperature at a high speed (5000r/min) for 30s, placing the hydrophobic PDMS soft template in the step (5) on the PDMS layer after the spin coating is finished, placing the PDMS soft template in a vacuum drier, vacuumizing for 2min, taking out the sample, and placing the sample in an oven at 80 ℃ for heating for 1 h. And taking out the sample, slightly stripping the PDMS soft template to obtain a structure for forming the grating layer on the photonic crystal layer, and thus obtaining the photonic crystal and grating composite optical structure anti-counterfeit label. Wherein, the thickness of the grating layer is about 6 μm, the period of the grating is 750nm, and the depth of the grating structure is about 100 nm.
According to the SEM image of the composite optical structure composed of the two-dimensional photonic crystal and the one-dimensional grating, the anti-counterfeit label prepared in example 2 can show different colors under different angles, for example, under the condition that the angle variation range is 6-80 degrees. Wherein, under the conditions that the incident angle of a light source is 25 degrees and the variation range of the observation angle is 6-14 degrees, the structural color of the grating in the prepared anti-counterfeiting label with the composite optical structure is observed to undergo the change from purple to blue. If the observation angle changes within the range of 6-11 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be purple; under the condition that the observation angle variation range is 12-14 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be blue; and observing the composite structure color of the photonic crystal and the grating in the prepared composite optical structure anti-counterfeiting label under the conditions that the incident angle of a light source is 25 degrees and the angle change range is 15-38 degrees. Under the conditions that the incident angle of a light source is 25 degrees and the angle variation range is 40-80 degrees, the structural color of the photonic crystal in the prepared composite optical structure anti-counterfeiting label is observed to undergo the change from yellow to red. If the angle variation range is 40-48 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be yellow; under the condition that the angle variation range is 49-55 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be orange; under the condition that the angle variation range is 56-80 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be red. Thus, forgery prevention can be achieved by changing the viewing angle and thus the observed color.
Example 3
This example illustrates a composite optical security label made in accordance with the present invention.
(1) And (3) putting 4mL of tetrabutyl titanate and 18mL of absolute ethyl alcohol into a conical flask, uniformly mixing, slowly dropwise adding 2mL of glacial acetic acid into the mixed solution, sealing the flask opening after dropwise adding is finished, and stirring for 5 hours at room temperature.
(2) 35mg of graphene oxide is weighed and placed in a beaker, 35mL of deionized water is added, and the solution is placed in an ultrasonic cell crusher to be subjected to ultrasonic treatment for 3 hours under the conditions of working for 2 seconds and intermittent operation for 3 seconds. Then the solution is placed in an ultrasonic cleaner to continue the ultrasonic treatment for 12 hours.
(3) Diluting the prepared titanium dioxide sol to a certain concentration by using ethanol, alternately spin-coating the graphene oxide solution and the titanium dioxide sol on a hydrophilic silicon wafer, coating one layer of the graphene oxide solution and the titanium dioxide sol on each silicon wafer, and heating the silicon wafer in a 60 ℃ oven for 10 min. The photon forbidden band position of the photonic crystal at 0 deg. of this example is 554 nm.
(4) Removing the printing layer, the protective layer and the reflecting layer on the CD, washing with ethanol, drying with nitrogen, and mixing the component A and the component B of PDMS in a weight ratio of 10: 1, uniformly mixing and fully stirring, and then putting the mixture into a centrifuge to centrifuge for 5min at a speed of 3000r/min so as to remove bubbles generated in the mixing process. And casting the prepared PDMS on the surface of the CD template, putting the sample in a vacuum drier, vacuumizing for 30min, taking out the sample, and putting the sample in an oven at 80 ℃ for heating for 2 h. And after cooling to room temperature, slightly stripping the PDMS from the CD template to obtain the PDMS soft template.
(5) Cutting the soft template obtained in the step (4) into a proper size, putting the soft template into a vacuum drier, dropwise adding a proper amount of fluorosilane into the soft template, vacuumizing the soft template for 20min, putting the soft template into an oven with the temperature of 80 ℃, heating the soft template for 2h, and performing hydrophobic treatment.
(6) Transferring 200 mu L of prepared PDMS by using a liquid transfer gun, spin-coating the transferred PDMS on the photonic crystal layer in the step (3) by using a KW-4A type spin coater, and keeping the transferred PDMS at a low speed (500r/min) for 5 s; keeping the temperature at a high speed (5000r/min) for 30s, placing the hydrophobic PDMS soft template in the step (5) on the PDMS layer after the spin coating is finished, placing the PDMS soft template in a vacuum drier, vacuumizing for 2min, taking out the sample, and placing the sample in an oven at 80 ℃ for heating for 1 h. And taking out the sample, slightly stripping the PDMS soft template to obtain a structure for forming the grating layer on the photonic crystal layer, and thus obtaining the photonic crystal and grating composite optical structure anti-counterfeit label. Wherein, the thickness of the grating layer is about 6 μm, the period of the grating is 1500nm, and the depth of the grating structure is about 120 nm.
According to the SEM image of the composite optical structure composed of the one-dimensional photonic crystal and the one-dimensional grating, the anti-counterfeit label prepared in example 3 can show different colors under different angles, for example, under the condition that the angle variation range is 0 ° to 90 °. Wherein, under the conditions that the incident angle of a light source is 0 DEG and the variation range of an observation angle is 0-10 DEG, the structural color of the photonic crystal in the prepared anti-counterfeiting label with the composite optical structure is observed, and the color is yellow-green; under the conditions that the incident angle of a light source is 0 degree and the angle change range is 16-90 degrees, the structural color of the grating in the prepared anti-counterfeiting label with the composite optical structure is observed to be changed from purple to red twice. If the angle variation range is 16-19 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be blue; under the condition that the angle variation range is 19-23 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be green; under the condition that the angle variation range is 25-32 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be red. Under the condition that the angle variation range is 33-40 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be blue; under the condition that the angle variation range is 41-50 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be green; under the condition that the angle variation range is 56-90 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be red. Thus, forgery prevention can be achieved by changing the viewing angle and thus the observed color.
Example 4
This example illustrates a composite optical security label made in accordance with the present invention.
(1) Cutting a 6cm multiplied by 4cm PET film, cleaning and carrying out hydrophilic treatment; fully performing ultrasonic treatment on 20 mass percent of monodisperse silicon dioxide globule solution with the particle size of 240nm to uniformly disperse the monodisperse silicon dioxide globule solution;
(2) fixing a PET film on a platform of an automatic film coating machine, using a liquid transfer gun to transfer 50 mu L of silicon dioxide pellet solution in the solution (1), dripping the silicon dioxide pellet solution on the surface of the PET film, setting the blade coating speed to be 10mm/s and the blade coating length to be 50mm, enabling a wire bar of the automatic film coating machine to scrape the surface of the PET film to form a liquid film, and naturally drying the liquid film at room temperature;
(3) the PET film coated with colloidal photonic crystals (silica pellets) by knife coating was placed in an oven at 80 ℃ and annealed for 1 hour to firmly bond the pellets to the PET film substrate, thereby forming a photonic crystal layer having a thickness of about 6 μm on the substrate. The position of the photon forbidden band of the photonic crystal at 0 deg. in this embodiment is 564 nm.
(4) Separating the upper layer and the lower layer of the DVD disc, flushing the lower layer with ethanol, blow-drying with nitrogen, and cutting into 1cm × 1 cm.
(5) Keeping the temperature for 5s at low speed (500r/min) by using a KW-4A type spin coater; and (4) spin-coating a polystyrene film on the photonic crystal layer in the step (3) under the condition of keeping the speed for 30s at 2500r/min, placing the DVD disk in the step (4) on the spin-coated polystyrene layer after the spin-coating is finished, and heating the DVD disk in an oven at the temperature of 80 ℃ for 1 h. And taking out the sample, and slightly stripping the DVD disc to obtain a structure of forming a grating layer on the photonic crystal layer, thereby obtaining the photonic crystal and grating composite optical structure anti-counterfeiting label. Wherein, the thickness of the grating layer is about 6 μm, the period of the grating is 750nm, and the depth of the grating structure is about 100 nm.
Example 4 the security label prepared can exhibit different colors at different angles, for example, at angles ranging from 0 ° to 90 °. Wherein, under the conditions that the incident angle of a light source is 0 DEG and the variation range of an observation angle is 0-10 DEG, the structural color and the green of the photonic crystal in the prepared anti-counterfeiting label with the composite optical structure are observed; under the conditions that the incident angle of a light source is 0 degrees and the angle change range is 30-90 degrees, the structural color of the grating in the prepared composite optical structure anti-counterfeiting label is observed to change from purple to red. If the angle variation range is 37-40 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be blue; under the condition that the angle variation range is 41-50 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be green; under the condition that the angle variation range is 56-90 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be red. Thus, forgery prevention can be achieved by changing the viewing angle and thus the observed color.
Example 5
This example illustrates a composite optical security label made in accordance with the present invention.
A composite optical film was prepared in the same manner as in example 1, except that 20nm Au was deposited on the surface by vapor deposition after the PDMS imprint template was peeled off in step 6.
The anti-counterfeit label prepared in example 5 can show different colors under different angles, for example, under the condition that the angle changes from 0 to 90 degrees. Wherein, under the conditions that the incident angle of a light source is 0 DEG and the variation range of an observation angle is 0-10 DEG, the structural color and the green of the photonic crystal in the prepared anti-counterfeiting label with the composite optical structure are observed; under the conditions that the incident angle of a light source is 0 degrees and the angle change range is 30-90 degrees, the structural color of the grating in the prepared composite optical structure anti-counterfeiting label is observed to change from purple to red. If the angle variation range is 37-40 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be blue; under the condition that the angle variation range is 41-50 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be green; under the condition that the angle variation range is 56-90 degrees, the prepared composite optical structure anti-counterfeiting label is observed to be red. Thus, forgery prevention can be achieved by changing the viewing angle and thus the observed color.
Example 6
This example illustrates a composite optical security label made in accordance with the present invention.
A composite optical film was prepared in the same manner as in example 1, except that a "star" pattern was rubbed on the DVD disc before the PDMS was poured onto the disc in step 4.
Fig. 6 is a schematic diagram of the colors of the anti-counterfeit label with a composite optical structure prepared in example 6 at different angles, from which it can be seen that the anti-counterfeit label shows different colors at different angles, for example, under the condition that the angle changes from 0 ° to 90 °, wherein the picture marked with "1" is green as a whole, the picture marked with "2" is a blue "star" pattern, and the picture marked with "3" is a green "star" pattern; the picture labeled "4" is in an orange "star" pattern. Obviously, the 'star' pattern in the anti-counterfeiting mark can be changed along with the change of the angle from hiding to showing, and can be in iridescence.
Example 7
This example illustrates a composite optical security label made in accordance with the present invention.
A composite optical film was prepared in the same manner as in example 6, except that a pattern of "stars" and a pattern of "moon" were erased on the DVD disc, respectively. And two PDMS imprinting templates with patterns are respectively placed at 2 positions of the spin-coated PDMS layer, and the directions of the imprinted grating grooves are different.
Fig. 7 is a schematic view of the composite optical structure security label prepared in example 7 showing the pattern change at different placement angles. The grating groove direction of the initially imprinted pattern is shown in the picture labeled "1" in fig. 7. Fixing an angle at which the hidden pattern can be observed, such as 40 °, from which the pattern change of the anti-counterfeiting mark under different placing angles can be seen, for example, when the placing angle is 0 °, observing a pattern of "moon", such as a picture marked with "2" in fig. 7; when the placing angle is 90 degrees, the pattern of the star is observed. Obviously, different patterns can be observed under the conditions of different placing angles of the anti-counterfeiting mark.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A composite optical structure, comprising: the photonic crystal structure includes a substrate, a photonic crystal layer formed on the substrate, and a grating layer formed on the photonic crystal layer.
2. The composite optical structure of claim 1 wherein the photonic crystal layer comprises one or more of a one-dimensional photonic crystal, a two-dimensional photonic crystal, and a three-dimensional photonic crystal.
3. The composite optical structure of claim 2, wherein the photonic crystal has a photon forbidden band in the range of 300-1500 nm;
preferably, the photon forbidden band range of the photonic crystal is 380-780 nm.
4. The composite optical structure according to any one of claims 1 to 3, wherein the photonic crystal layer is a one-dimensional photonic crystal layer, a two-dimensional photonic crystal layer, or a three-dimensional photonic crystal layer;
preferably, the one-dimensional photonic crystal layer is prepared by one or more methods selected from an alternating coating method, a spin coating method, a spraying method, a pulling method, an LB film technology and a layer-by-layer stacking technology;
preferably, the two-dimensional photonic crystal layer is prepared by one or more methods selected from a self-assembly method, an etching method and a multi-beam interference method;
preferably, the three-dimensional photonic crystal layer is prepared by one or more methods selected from a self-assembly method, a layer-by-layer stacking technique, a holographic lithography method and a sacrificial template method.
5. The composite optical structure of any of claims 1-4, wherein the grating layer comprises a one-dimensional grating and/or a two-dimensional grating;
preferably, the groove shape of the grating is sinusoidal, rectangular or sawtooth.
6. The composite optical structure of any of claims 1-5, wherein the grating layer is film-like;
preferably, the grating layer is prepared by one or more methods selected from holographic interferometry, electron beam exposure, focused ion beam processing, optical lithography, two-beam interferometry, laser direct writing, and nanoimprint.
7. The composite optical structure according to any of claims 1-6, wherein the material of the grating layer is an organic material and/or an inorganic material;
preferably, the material of the grating layer is PMMA, PDMS, PS, PVA, Ag, Al and Al 2 O 3 One or more of;
preferably, the thickness of the grating layer is 200nm-20 μm, preferably 200nm-10 μm;
preferably, the period of the grating is 400nm-20 μm, preferably 700-1500 nm.
8. A method of making a composite optical structure, comprising the steps of,
1) a step of forming a photonic crystal layer on a substrate;
2) and forming a grating layer on the photonic crystal layer.
9. A security label comprising a composite optical structure according to any one of claims 1 to 7.
10. Use of a composite optical structure according to any one of claims 1 to 7 in the field of anti-counterfeiting.
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