CN115373057A - Structural color film with high mechanical stability and preparation method and application thereof - Google Patents
Structural color film with high mechanical stability and preparation method and application thereof Download PDFInfo
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- CN115373057A CN115373057A CN202210285633.6A CN202210285633A CN115373057A CN 115373057 A CN115373057 A CN 115373057A CN 202210285633 A CN202210285633 A CN 202210285633A CN 115373057 A CN115373057 A CN 115373057A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention relates to the field of structural colors, and discloses a structural color film with high mechanical stability, and a preparation method and application thereof. The structural color film with high mechanical stability comprises a frame base layer and a structural color layer, wherein the frame base layer is provided with more than one groove, and the structural color layer is formed in the groove; the structure color layer is provided with a micro-nano structure, and the micro-nano structure can interact with light to generate a structure color. According to the invention, the structural color film with high mechanical stability, and the preparation method and the application thereof can be provided.
Description
Technical Field
The invention relates to the field of structural colors, in particular to a structural color film with high mechanical stability and a preparation method and application thereof.
Background
Structural colors are very common in nature and life. Structural color (structural color), unlike dyes: also called physical color, is a color generated by interaction of light with the micro-nano structure such as refraction, reflection, diffraction or interference. The principle of structural color generation is: when a beam of visible light (with the wavelength of 400nm-800nm generally) irradiates on the micro-nano structure of a substance, the light with the wavelength matched with the size of the micro-nano structure can be selectively reflected or scattered back by the micro-nano structure, so that the surface of the substance with the micro-nano structure can generate a specific color, and a structural color is generated.
Structural colors are a very common color representation in nature and are almost ubiquitous. The blue color of the sky under a clear sky is generally considered to be derived from rayleigh scattering, the color of oil stains on the water surface is derived from thin film interference, the rainbow is derived from refraction, the metallic luster and glitter of the beetle body wall surface, the color of bird feathers, the color of butterfly wings, and the like are typical structural colors. The structural color depends on the micro-nano structure of the substance, is more stable and environment-friendly compared with dye, and can not fade as long as the micro-nano structure is not damaged.
The existing structural color is generated by interference, diffraction and scattering of light waves by a micro-nano structure, but the micro-nano structure is easy to damage when being worn, so that the structural color is lost. The present invention thus discloses a method for preparing a frame structure with high mechanical stability, which protects the internal color-generating structure from wear, so as to enhance the mechanical strength of the structural color coating.
The currently common method for preparing high mechanical strength structural color coatings is to target the nanoparticlesModifying to form chemical bonds among the nano particles to increase the adhesion among the nano particles; and secondly, the contact area among the nano particles is increased, and the structural strength is increased. For example, the PDA @ SiO is prepared in the documents Nanoscale,2018,10,3673-3679 2 The structure is characterized in that an amorphous array is prepared by spraying, and the dopamine shell layer structure is further oxidized and crosslinked by alkali steam treatment to obtain the high-strength photonic crystal. In the document Macromol, rapid, commun, 2007,28, 1987-1994, polymethyl methacrylate is taken as a core, epoxypropyl methacrylate is taken as a shell layer, after an ordered structure is assembled, ring-opening polymerization reaction is carried out under thermal initiation, so that chemical bonding is formed at bonding points among microspheres, and the bonding force among the microspheres is increased. In the literature, macromol. Chem. Phys.2006,207,596-604, P (St-MMA-AA) core-shell structures with PS as hard core and PMMA/PAA as elastic layer were prepared. The core-shell structure microspheres are assembled under the heating condition to obtain close packing, the shell layers can be softened and form hydrogen bond action, air between the microspheres is replaced by the shell layer structure, and the mechanical stability is greatly improved. In the previous methods, the characteristics of the microspheres are changed by doping different components, and the adhesion force is increased on a small scale, but the preparation processes of the methods are complex.
Therefore, it is necessary to design a structural color film with simple preparation method, low cost, environmental friendliness and high mechanical stability.
Disclosure of Invention
The invention aims to solve the problems that a micro-nano structure of a structural color is easy to wear and damage and cannot be applied to actual life and production in the prior art, and provides a structural color film with high mechanical stability and a preparation method and application thereof.
In order to achieve the above object, an aspect of the present invention provides a structural color film with high mechanical stability, which includes a frame base layer having one or more grooves and a structural color layer formed in the grooves; the structure color layer is provided with a micro-nano structure, and the micro-nano structure can interact with light to generate a structure color.
Preferably, the groove of the frame base layer is one or more of a groove shape, a hemisphere shape, a bowl shape, an inverted pyramid shape, an inverted triangular pyramid shape, an inverted pyramid shape, and a square shape.
Preferably, the groove of the frame base layer is a groove, and the depth thereof is 0.1-5000 μm, preferably 1-1000 μm, and more preferably 2-100 μm.
Preferably, the grooves of the frame base layer have a hemispherical shape and a diameter of 0.1 to 5000. Mu.m, preferably 1 to 1000. Mu.m, and more preferably 2 to 100. Mu.m.
Preferably, the groove of the frame substrate is bowl-shaped, and has a diameter of 0.1-5000 μm, preferably 1-1000 μm, and more preferably 2-100 μm.
Preferably, the groove of the frame base layer has a side length of 0.1-5000 μm, preferably 1-1000 μm, and more preferably 2-100 μm when it is in an inverted pyramid shape.
Preferably, when the groove of the frame base layer is in the shape of an inverted pyramid, the side length is 0.1-5000 μm, preferably 1-1000 μm, and more preferably 2-100 μm.
Preferably, the groove of the frame base layer has a side length of 0.1 to 5000 μm, preferably 1 to 1000 μm, and more preferably 2 to 100 μm, when it has a square shape.
Preferably, the frame base layer is made of hard materials or flexible materials; more preferably, the material of the frame base layer is a composite material of any one or more of Si, PDMS, PMMA, PET, al and ceramic.
Preferably, the frame base layer is formed by one or more of an etching method, a stencil printing method, and a breathing pattern method.
Preferably, the structured color layer has a reflection peak position of the structured color of 200 to 2000nm, more preferably 310 to 1050nm, and further preferably 390 to 780nm.
Preferably, the micro-nano structure of the structure color layer comprises one or more of a film, a grating, a super surface, a photonic crystal, an amorphous photonic structure, a disordered structure and a composite structure.
Preferably, the film can produce structural color by interference, and the film includes a film formed of a transparent solid, a film formed of a liquid, a thin layer of a gas sandwiched by two pieces of glass, or a multilayer film in which multilayer interference occurs.
Preferably, the grating comprises a one-dimensional grating and/or a two-dimensional grating.
Preferably, the super-surface comprises one or more of a metal optical super-surface, a metal oxide optical super-surface, a nitride optical super-surface, and a high refractive index material super-surface.
Preferably, the photonic crystal comprises one or more of a one-dimensional photonic crystal, a two-dimensional photonic crystal and a three-dimensional photonic crystal.
Preferably, the one-dimensional photonic crystal is prepared by any one of an alternating coating method, a spin coating method, a spray coating method, a pulling method, an LB film technology, a layer-by-layer stacking technology, electron beam exposure, two-photon polymerization and 3D printing.
Preferably, the two-dimensional photonic crystal is prepared by any one of a self-assembly method, an etching method, a multi-beam interference method, two-photon polymerization, and 3D printing.
Preferably, the three-dimensional photonic crystal is prepared by any one of a self-assembly method, a layer-by-layer stacking technique, a holographic lithography method, a sacrificial template method, two-photon polymerization and 3D printing.
Preferably, the amorphous photonic structure is a short-range ordered long-range disordered quasiperiodic structure.
Preferably, the structural color produced by the disordered structure scattering is Rayleigh scattering and Mie scattering.
Preferably, the composite structure is produced by utilizing the composite action of a plurality of structures, and multifunctional structural colors with iridescence effect, polarization effect, high saturation and high brightness can be realized.
Preferably, the structural colour layer is covered with a layer of transparent material.
Preferably, the transparent material in the transparent material layer is one or more of silk fibroin, cellulose, starch, polyimide, epoxy resin, light-cured glue, varnish, PMMA, PDMS and PET.
According to a second aspect of the present invention, there is provided a method for preparing a structural color thin film with high mechanical stability, wherein the method comprises the steps of,
1) A step of preparing a frame base layer having one or more grooves;
2) A step of forming a structural color layer in the groove,
the structure color layer is provided with a micro-nano structure, and the micro-nano structure can interact with light to generate a structure color.
Preferably, the groove of the frame base layer is one or more of a groove shape, a hemisphere shape, a bowl shape, an inverted pyramid shape, an inverted triangular pyramid shape, an inverted pyramid shape, and a square shape.
Preferably, the groove of the frame base layer is a groove, and the depth thereof is 0.1-5000 μm, preferably 1-1000 μm, and more preferably 2-100 μm.
Preferably, the grooves of the frame base layer have a hemispherical shape and a diameter of 0.1 to 5000. Mu.m, preferably 1 to 1000. Mu.m, and more preferably 2 to 100. Mu.m.
Preferably, the groove of the frame substrate has a bowl shape, and the diameter of the bowl shape is 0.1-5000 μm, preferably 1-1000 μm, and more preferably 2-100 μm.
Preferably, the groove of the frame base layer has a side length of 0.1-5000 μm, preferably 1-1000 μm, and more preferably 2-100 μm when it is in the shape of an inverted pyramid.
Preferably, the groove of the frame base layer has a side length of 0.1-5000 μm, preferably 1-1000 μm, and more preferably 2-100 μm when it is in the shape of an inverted frustum of a pyramid.
Preferably, the groove of the frame base layer has a side length of 0.1 to 5000 μm, preferably 1 to 1000 μm, and more preferably 2 to 100 μm, when it has a square shape.
Preferably, the frame base layer is made of hard materials or flexible materials; more preferably, the material of the frame base layer is a composite material of any one or more of Si, PDMS, PMMA, PET, al and ceramic.
Preferably, the frame base layer is formed by one or more of an etching method, a stencil printing method, and a respiratory pattern method.
Preferably, the structured color layer has a reflection peak position of the structured color of 200 to 2000nm, more preferably 310 to 1050nm, and further preferably 390 to 780nm.
Preferably, the micro-nano structure of the structure color layer comprises one or more of a film, a grating, a super surface, a photonic crystal, an amorphous photonic structure, a disordered structure and a composite structure.
Preferably, the film can produce structural color by interference, and the film includes a film formed of a transparent solid, a film formed of a liquid, a thin layer of a gas sandwiched by two pieces of glass, or a multilayer film in which multilayer interference occurs.
Preferably, the grating comprises a one-dimensional grating and/or a two-dimensional grating.
Preferably, the super-surface comprises one or more of a metal optical super-surface, a metal oxide super-surface, a nitride super-surface and a super-surface of other high refractive index materials.
Preferably, the photonic crystal comprises one or more of a one-dimensional photonic crystal, a two-dimensional photonic crystal and a three-dimensional photonic crystal.
Preferably, the one-dimensional photonic crystal is prepared by any one of an alternating coating method, a spin coating method, a spray coating method, a pulling method, an LB film technology, a layer-by-layer stacking technology, electron beam exposure, two-photon polymerization and 3D printing.
Preferably, the two-dimensional photonic crystal is prepared by any one of a self-assembly method, an etching method, a multi-beam interference method, two-photon polymerization, and 3D printing.
Preferably, the three-dimensional photonic crystal is prepared by any one of a self-assembly method, a layer-by-layer stacking technique, a holographic lithography method, a sacrificial template method, two-photon polymerization and 3D printing.
Preferably, the amorphous photonic structure is a short-range ordered long-range disordered quasiperiodic structure.
Preferably, the structural color produced by the disordered structure scattering is Rayleigh scattering and Mie scattering.
Preferably, the composite structure is produced by utilizing the composite action of a plurality of structures, and multifunctional structural colors with iridescence effect, polarization effect, high saturation and high brightness can be realized.
Preferably, the method further comprises the step of forming a layer of transparent material on the structural color layer.
Preferably, the transparent material used for forming the transparent material layer is one or more of silk fibroin, cellulose, starch, polyimide, epoxy resin, light-cured glue, varnish, PMMA, PDMS and PET.
According to the third aspect of the invention, the high-mechanical-stability structural color film prepared by the preparation method of the high-mechanical-stability structural color film is provided.
According to a fourth aspect of the present invention, there is provided an application of the structural color film with high mechanical stability of the present invention or the structural color film with high mechanical stability prepared by the method of the present invention in wearable, display, package decoration, sensing and anti-counterfeiting.
Through the technical scheme, the invention has the advantages that:
1) The frame base layer provided by the invention is provided with the groove structure, so that a fragile color-generating structure (micro-nano structure) in the frame base layer can be protected, the integral mechanical strength is improved, and the structural color can be better applied to life production.
2) The high-mechanical-stability structural color film provided by the invention solves the problem that the structural color is easily influenced by external conditions, and provides a wider idea for the fields of coating, sensing, displaying and the like of the structural color.
3) The method is environment-friendly, simple and quick, has short preparation period and can be used for large-area preparation.
Drawings
Fig. 1 is an SEM image of a structural color thin film with high mechanical stability having a groove-like structure in which a plurality of grooves are filled with a photo crystal obtained in example 1.
FIG. 2 is a SEM cross-sectional view of a trench-like structure with a photonic crystal assembled.
FIG. 3 is a comparison of structural colors of the structural color film prepared in example 1 before and after rubbing.
FIG. 4 is an optical microscope photograph of the high mechanical stability structured color film having a hemispherical groove structure with a plurality of optical crystals assembled inside the hemispherical grooves obtained in example 2.
Fig. 5 is an SEM image of a hemispherical structure with a photonic crystal assembled therein in fig. 4.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are given by way of illustration and explanation only, not limitation.
In the present invention, the structural color is also called physical color, which is a gloss caused by the wavelength of light. Are colors produced by light waves refracted, diffusely reflected, diffracted, or interfered by the microstructures. The structural color may be generated by one or more of thin film interference, gratings, super-surfaces, photonic crystals, amorphous photonic structures, disordered structures (structural colors generated by disordered structure scattering such as rayleigh scattering and mie scattering), composite structures, and the like.
In the present invention, the structural color layer refers to a layer having a micro-nano structure and capable of generating a structural color by refraction, diffuse reflection, diffraction or interference of light, and may include, for example, a grating, a surface plasmon thin film, a photonic crystal, and the like.
According to a first aspect of the present invention, there is provided a high mechanical stability structural color film comprising a frame base layer having one or more grooves and a structural color layer formed in the grooves; the structure color layer is provided with a micro-nano structure, and the micro-nano structure can interact with light to generate a structure color.
According to the film, the groove of the frame base layer is one or more of a groove shape, a semispherical shape, a bowl shape, an inverted pyramid shape, an inverted triangular pyramid shape, an inverted frustum of pyramid shape and a cube shape; preferably, the groove of the frame base layer is one or more of a groove shape, a hemisphere shape and a bowl shape; more preferably, the groove of the frame base layer is groove-shaped and/or hemispherical.
According to the film of the present invention, the structural color layer is formed in the groove, and preferably, the edge of the groove is higher than the structural color layer or is substantially on the same surface as the surface of the structural color layer.
According to the film of the present invention, when the groove of the frame base layer is groove-shaped, the depth thereof is preferably 0.1 to 5000 μm, preferably 1 to 1000 μm, and more preferably 2 to 100 μm. The depth thereof may be, for example: 0.1 μm, 0.2 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 5 μm, 12 μm, 15 μm, 20 μm, 22 μm, 25 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm, 58 μm, 60 μm, 62 μm, 65 μm, 68 μm, 70 μm, or 72 μm, 75 μm, 78 μm, 80 μm, 82 μm, 85 μm, 88 μm, 90 μm, 92 μm, 95 μm, 98 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, 160 μm, 165 μm, 170 μm, 175 μm, 180 μm 185 μm, 190 μm, 195 μm, 200 μm, 210 μm, 230 μm, 250 μm, 280 μm, 300 μm, 310 μm, 330 μm, 350 μm, 380 μm, 400 μm, 410 μm, 430 μm, 450 μm, 480 μm, 500 μm, 510 μm, 530 μm, 550 μm, 580 μm, 600 μm, 610 μm, 630 μm, 650 μm, 680 μm, 700 μm, 710 μm, 730 μm, 750 μm, 780 μm, 800 μm, 810 μm, 830 μm, 850 μm, 880 μm, 900 μm, 910 μm, 930 μm, 950 μm, 980 μm, 1000 μm, 1100 μm, 1500 μm, 2000 μm, 2500 μm, 3000 μm, 3500 μm, 4000 μm, 4500 μm, 5000 μm and the like.
According to the film of the present invention, preferably, when the groove of the frame base layer is hemispherical, the diameter thereof is 0.1 to 5000 μm, preferably 1 to 1000 μm, and more preferably 2 to 100 μm. The diameters thereof may be, for example: 0.1 μm, 0.2 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 5 μm, 12 μm, 15 μm, 20 μm, 22 μm, 25 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm, 58 μm, 60 μm, 62 μm, 65 μm, 68 μm, 70 μm, or 72 μm, 75 μm, 78 μm, 80 μm, 82 μm, 85 μm, 88 μm, 90 μm, 92 μm, 95 μm, 98 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, 160 μm, 165 μm, 170 μm, 175 μm, 180 μm 185 μm, 190 μm, 195 μm, 200 μm, 210 μm, 230 μm, 250 μm, 280 μm, 300 μm, 310 μm, 330 μm, 350 μm, 380 μm, 400 μm, 410 μm, 430 μm, 450 μm, 480 μm, 500 μm, 510 μm, 530 μm, 550 μm, 580 μm, 600 μm, 610 μm, 630 μm, 650 μm, 680 μm, 700 μm, 710 μm, 730 μm, 750 μm, 780 μm, 800 μm, 810 μm, 830 μm, 850 μm, 880 μm, 900 μm, 910 μm, 930 μm, 950 μm, 980 μm, 1000 μm, 1100 μm, 1500 μm, 2000 μm, 2500 μm, 3000 μm, 3500 μm, 4000 μm, 4500 μm, 5000 μm and the like.
According to the film of the present invention, the groove of the frame base layer is preferably bowl-shaped and has a diameter of 0.1 to 5000 μm, preferably 1 to 1000 μm, and more preferably 2 to 100 μm. The diameters thereof may be, for example: 0.1 μm, 0.2 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 5 μm, 12 μm, 15 μm, 20 μm, 22 μm, 25 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm, 58 μm, 60 μm, 62 μm, 65 μm, 68 μm, 70 μm 72 μm, 75 μm, 78 μm, 80 μm, 82 μm, 85 μm, 88 μm, 90 μm, 92 μm, 95 μm, 98 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, 160 μm, 165 μm, 170 μm, 175 μm, 180 μm 185, 190, 195, 200, 210, 230, 250, 280, 300, 310, 330, 350, 380, 400, 410, 430, 450, 480, 500, 510, 530, 550, 580, 600, 610, 630, 650, 680, 700, 710, 730, 750, 780, 800, 810, 830, 850, 880, 900, 910, 930, 950, 980, 1000, 1100, 1500, 2000, 2500, 3000, 3500, 4500, 5000, etc.
According to the film of the present invention, preferably, when the groove of the frame base layer is in the shape of an inverted pyramid, the side length thereof is 0.1 to 5000 μm, preferably 1 to 1000 μm, and more preferably 2 to 100 μm. The side lengths may be, for example: 0.1 μm, 0.2 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 5 μm, 12 μm, 15 μm, 20 μm, 22 μm, 25 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm, 58 μm, 60 μm, 62 μm, 65 μm, 68 μm, 70 μm, or 72 μm, 75 μm, 78 μm, 80 μm, 82 μm, 85 μm, 88 μm, 90 μm, 92 μm, 95 μm, 98 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, 160 μm, 165 μm, 170 μm, 175 μm, 180 μm 185 μm, 190 μm, 195 μm, 200 μm, 210 μm, 230 μm, 250 μm, 280 μm, 300 μm, 310 μm, 330 μm, 350 μm, 380 μm, 400 μm, 410 μm, 430 μm, 450 μm, 480 μm, 500 μm, 510 μm, 530 μm, 550 μm, 580 μm, 600 μm, 610 μm, 630 μm, 650 μm, 680 μm, 700 μm, 710 μm, 730 μm, 750 μm, 780 μm, 800 μm, 810 μm, 830 μm, 850 μm, 880 μm, 900 μm, 910 μm, 930 μm, 950 μm, 980 μm, 1000 μm, 1100 μm, 1500 μm, 2000 μm, 2500 μm, 3000 μm, 3500 μm, 4000 μm, 4500 μm, 5000 μm and the like. Here, the side length refers to a height of the inverted pyramid-shaped groove.
According to the film of the present invention, preferably, the groove of the frame base layer has a side length of 0.1 to 5000 μm, preferably 1 to 1000 μm, and more preferably 2 to 100 μm, when it has an inverted truncated pyramid shape. The side lengths may be, for example: 0.1 μm, 0.2 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 5 μm, 12 μm, 15 μm, 20 μm, 22 μm, 25 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm, 58 μm, 60 μm, 62 μm, 65 μm, 68 μm, 70 μm, or 72 μm, 75 μm, 78 μm, 80 μm, 82 μm, 85 μm, 88 μm, 90 μm, 92 μm, 95 μm, 98 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, 160 μm, 165 μm, 170 μm, 175 μm, 180 μm 185 μm, 190 μm, 195 μm, 200 μm, 210 μm, 230 μm, 250 μm, 280 μm, 300 μm, 310 μm, 330 μm, 350 μm, 380 μm, 400 μm, 410 μm, 430 μm, 450 μm, 480 μm, 500 μm, 510 μm, 530 μm, 550 μm, 580 μm, 600 μm, 610 μm, 630 μm, 650 μm, 680 μm, 700 μm, 710 μm, 730 μm, 750 μm, 780 μm, 800 μm, 810 μm, 830 μm, 850 μm, 880 μm, 900 μm, 910 μm, 930 μm, 950 μm, 980 μm, 1000 μm, 1100 μm, 1500 μm, 2000 μm, 2500 μm, 3000 μm, 3500 μm, 4000 μm, 4500 μm, 5000 μm and the like. Here, the side length refers to the height of the inverted truncated pyramid-shaped groove.
According to the film of the present invention, preferably, the groove of the frame base layer has a side length of 0.1 to 5000 μm, preferably 1 to 1000 μm, and more preferably 2 to 100 μm, when it is in a square shape. The side lengths may be, for example: 0.1 μm, 0.2 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 5 μm, 12 μm, 15 μm, 20 μm, 22 μm, 25 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm, 58 μm, 60 μm, 62 μm, 65 μm, 68 μm, 70 μm, or 72 μm, 75 μm, 78 μm, 80 μm, 82 μm, 85 μm, 88 μm, 90 μm, 92 μm, 95 μm, 98 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, 160 μm, 165 μm, 170 μm, 175 μm, 180 μm 185 μm, 190 μm, 195 μm, 200 μm, 210 μm, 230 μm, 250 μm, 280 μm, 300 μm, 310 μm, 330 μm, 350 μm, 380 μm, 400 μm, 410 μm, 430 μm, 450 μm, 480 μm, 500 μm, 510 μm, 530 μm, 550 μm, 580 μm, 600 μm, 610 μm, 630 μm, 650 μm, 680 μm, 700 μm, 710 μm, 730 μm, 750 μm, 780 μm, 800 μm, 810 μm, 830 μm, 850 μm, 880 μm, 900 μm, 910 μm, 930 μm, 950 μm, 980 μm, 1000 μm, 1100 μm, 1500 μm, 2000 μm, 2500 μm, 3000 μm, 3500 μm, 4000 μm, 4500 μm, 5000 μm and the like.
Further, in the present invention, the opening width of the groove of the frame base layer may be 0.1 to 5000 μm, preferably 1 to 1000 μm, more preferably 2 to 200 μm, and still more preferably 10 to 150 μm.
According to the film disclosed by the invention, the frame base layer can be made of a hard material or a flexible material; preferably, the material of the frame base layer is a composite material of any one or more of Si, PDMS (polydimethylsiloxane), PMMA (polymethyl methacrylate), PET (polyethylene terephthalate), al and ceramic.
According to the thin film of the present invention, preferably, the frame base layer may be formed by one or more of an etching method, a stencil printing method, and a respiratory pattern method.
The etching method is a method of performing engraving etching on the surface of a substrate by using a physical or chemical method to pattern the substrate, such as wet etching of a silicon wafer, electron beam etching, focused ion beam lithography, and the like.
The template imprinting method is a technique of transferring a structure on a template to a material to be processed through a material having thermoplasticity or photoplasticity, such as polydimethylsiloxane, photoresist, or the like.
The respiratory pattern method is a micro-nano structure processing method, and is a method for forming a periodic polymer pore structure by utilizing a liquid drop array formed by condensing water vapor or other steam on the surface of a polymer solution and sequentially volatilizing a polymer solvent and liquid drops.
Specific conditions of the etching method, the template imprinting method, and the breathing pattern method are not particularly limited, and those skilled in the art may specifically select the etching method, the template imprinting method, and the breathing pattern method according to a desired framework base structure.
According to the film of the present invention, preferably, the structural color of the structural color layer has a reflection peak position of 200 to 2000nm, preferably 310 to 1050nm, more preferably 390 to 780nm.
According to the film, the micro-nano structure of the structural color layer comprises one or more of a film, a grating, a super surface, a photonic crystal, an amorphous photonic structure, a disordered structure and a composite structure.
Preferably, the film comprises a film formed of a transparent solid, a film formed of a liquid, a thin layer of a gas sandwiched by two pieces of glass, or a multilayer film in which multilayer interference can occur.
Preferably, the grating comprises a one-dimensional grating and/or a two-dimensional grating.
Preferably, the super-surface comprises one or more of a metal optical super-surface, a metal oxide super-surface, a nitride super-surface and a high refractive index material super-surface.
The metal oxide super surface may be, for example, tiO 2 Super-surface, etc.
The nitride super-surface may be, for example, a TiN super-surface.
The high refractive index material super-surface may be, for example, a silicon super-surface.
Preferably, the photonic crystal comprises one or more of a one-dimensional photonic crystal, a two-dimensional photonic crystal and a three-dimensional photonic crystal.
In the invention, the one-dimensional photonic crystal is a multilayer film which has dielectric constant periodic arrangement in one direction and mainly comprises different medium periodic arrangement. For example, the film can be prepared by any one of an alternating coating method, a spin coating method, a spray coating method, a pulling method, an LB film technology, a layer-by-layer stacking technology, electron beam exposure, two-photon polymerization and 3D printing.
The two-dimensional photonic crystal is formed by periodically arranging dielectric constants in two directions and mainly comprises a grating structure with characteristic dimension of wavelength magnitude, a two-dimensional lattice structure and the like. For example, it can be produced by any one of a self-assembly method, an etching method, a multi-beam interference method, two-photon polymerization, and 3D printing.
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 and the like. For example, the optical film can be prepared by any one of a self-assembly method, a layer-by-layer stacking technique, a holographic lithography method, a sacrificial template method, two-photon polymerization, and 3D printing.
Preferably, the amorphous photonic structure is a short-range ordered long-range disordered quasiperiodic structure. For example, spongy structures in parrot feathers (PNAS 2012 109 (27) 10798-10801), spongy structures in Nitraria Cotinga maynana hairs (Soft Matter,2009,5, 1792-1795), and fibrous structures of proteins in The same thickness, at equal distances and in parallel in The facial skin of Nitraria glauca (The Journal of Experimental Biology 207, 2157-2172).
Preferably, the structural color generated by the disordered structure scattering is Rayleigh scattering and Mie scattering, for example, blue on a dragonfly body is also derived from the uncorrelated scattering of light by scattering particles in the body.
Preferably, the composite structure is produced by utilizing the composite action of a plurality of structures, and multifunctional structural colors with iridescence, polarization effect, high saturation and high brightness can be realized.
According to the invention, the structured color layer is preferably covered with a transparent material layer, by means of which the surface of the high-mechanical-stability structured color film can be smoothed.
According to the present invention, preferably, the transparent material in the transparent material layer is one or more of silk fibroin, cellulose, starch, polyimide, epoxy resin, light-cured glue, varnish, PMMA, PDMS and PET.
According to a second aspect of the present invention, there is provided a method for preparing a structural color thin film with high mechanical stability, the method comprising the steps of,
1) A step of preparing a frame base layer having one or more grooves;
2) A step of forming a structural color layer in the groove,
the structure color layer is provided with a micro-nano structure, and the micro-nano structure can interact with light to generate a structure color.
According to the method, the groove of the frame base layer is in one or more of a groove shape, a hemispherical shape, a bowl shape, an inverted pyramid shape, an inverted triangular cone shape, an inverted pyramid shape and a cube shape; preferably, the groove of the frame base layer is one or more of a groove shape, a hemisphere shape and a bowl shape; more preferably, the groove of the frame base layer is groove-shaped and/or hemispherical.
According to the method of the present invention, the structural color layer is formed in the groove, preferably, the edge of the groove is higher than the structural color layer or the edge of the groove is substantially on the same surface as the surface of the structural color layer.
According to the method of the present invention, preferably, when the groove of the frame base layer is groove-shaped, the depth thereof is 0.1 to 5000 μm, preferably 1 to 1000 μm, and more preferably 2 to 100 μm. The depth thereof may be, for example: 0.1 μm, 0.2 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 5 μm, 12 μm, 15 μm, 20 μm, 22 μm, 25 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm, 58 μm, 60 μm, 62 μm, 65 μm, 68 μm, 70 μm, or 72 μm, 75 μm, 78 μm, 80 μm, 82 μm, 85 μm, 88 μm, 90 μm, 92 μm, 95 μm, 98 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, 160 μm, 165 μm, 170 μm, 175 μm, 180 μm 185, 190, 195, 200, 210, 230, 250, 280, 300, 310, 330, 350, 380, 400, 410, 430, 450, 480, 500, 510, 530, 550, 580, 600, 610, 630, 650, 680, 700, 710, 730, 750, 780, 800, 810, 830, 850, 880, 900, 910, 930, 950, 980, 1000, 1100, 1500, 2000, 2500, 3000, 3500, 4500, 5000, etc.
According to the method of the present invention, preferably, the grooves of the frame base layer have a diameter of 0.1 to 5000 μm, preferably 1 to 1000 μm, and more preferably 2 to 100 μm, when they are hemispherical. The diameters thereof may be, for example: 0.1 μm, 0.2 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 5 μm, 12 μm, 15 μm, 20 μm, 22 μm, 25 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm, 58 μm, 60 μm, 62 μm, 65 μm, 68 μm, 70 μm, 72 μm, 75 μm, 78 μm, 80 μm, 82 μm, 85 μm, 88 μm, 90 μm, 92 μm, 95 μm, 98 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, 160 μm, 170 μm, 175 μm, 180 μm, etc 185 μm, 190 μm, 195 μm, 200 μm, 210 μm, 230 μm, 250 μm, 280 μm, 300 μm, 310 μm, 330 μm, 350 μm, 380 μm, 400 μm, 410 μm, 430 μm, 450 μm, 480 μm, 500 μm, 510 μm, 530 μm, 550 μm, 580 μm, 600 μm, 610 μm, 630 μm, 650 μm, 680 μm, 700 μm, 710 μm, 730 μm, 750 μm, 780 μm, 800 μm, 810 μm, 830 μm, 850 μm, 880 μm, 900 μm, 910 μm, 930 μm, 950 μm, 980 μm, 1000 μm, 1100 μm, 1500 μm, 2000 μm, 2500 μm, 3000 μm, 3500 μm, 4000 μm, 4500 μm, 5000 μm and the like.
According to the film of the present invention, the groove of the frame base layer is preferably bowl-shaped and has a diameter of 0.1 to 5000 μm, preferably 1 to 1000 μm, and more preferably 2 to 100 μm. The diameters thereof may be, for example: 0.1 μm, 0.2 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 5 μm, 12 μm, 15 μm, 20 μm, 22 μm, 25 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm, 58 μm, 60 μm, 62 μm, 65 μm, 68 μm, 70 μm, 72 μm, 75 μm, 78 μm, 80 μm, 82 μm, 85 μm, 88 μm, 90 μm, 92 μm, 95 μm, 98 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, 160 μm, 170 μm, 175 μm, 180 μm, etc 185, 190, 195, 200, 210, 230, 250, 280, 300, 310, 330, 350, 380, 400, 410, 430, 450, 480, 500, 510, 530, 550, 580, 600, 610, 630, 650, 680, 700, 710, 730, 750, 780, 800, 810, 830, 850, 880, 900, 910, 930, 950, 980, 1000, 1100, 1500, 2000, 2500, 3000, 3500, 4500, 5000, etc.
According to the method of the present invention, preferably, the grooves of the frame base layer have an edge length of 0.1 to 5000 μm, preferably 1 to 1000 μm, and more preferably 2 to 100 μm, when they are in the shape of inverted pyramids. The side lengths may be, for example: 0.1 μm, 0.2 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 5 μm, 12 μm, 15 μm, 20 μm, 22 μm, 25 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm, 58 μm, 60 μm, 62 μm, 65 μm, 68 μm, 70 μm, 72 μm, 75 μm, 78 μm, 80 μm, 82 μm, 85 μm, 88 μm, 90 μm, 92 μm, 95 μm, 98 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, 160 μm, 170 μm, 175 μm, 180 μm, etc 185, 190, 195, 200, 210, 230, 250, 280, 300, 310, 330, 350, 380, 400, 410, 430, 450, 480, 500, 510, 530, 550, 580, 600, 610, 630, 650, 680, 700, 710, 730, 750, 780, 800, 810, 830, 850, 880, 900, 910, 930, 950, 980, 1000, 1100, 1500, 2000, 2500, 3000, 3500, 4500, 5000, etc. Here, the side length refers to a height of the inverted pyramid-shaped groove.
According to the method of the present invention, preferably, the groove of the frame base layer has a side length of 0.1 to 5000 μm, preferably 1 to 1000 μm, and more preferably 2 to 100 μm, when it has an inverted truncated pyramid shape. The side lengths may be, for example: 0.1 μm, 0.2 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 5 μm, 12 μm, 15 μm, 20 μm, 22 μm, 25 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm, 58 μm, 60 μm, 62 μm, 65 μm, 68 μm, 70 μm 72 μm, 75 μm, 78 μm, 80 μm, 82 μm, 85 μm, 88 μm, 90 μm, 92 μm, 95 μm, 98 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, 160 μm, 165 μm, 170 μm, 175 μm, 180 μm 185, 190, 195, 200, 210, 230, 250, 280, 300, 310, 330, 350, 380, 400, 410, 430, 450, 480, 500, 510, 530, 550, 580, 600, 610, 630, 650, 680, 700, 710, 730, 750, 780, 800, 810, 830, 850, 880, 900, 910, 930, 950, 980, 1000, 1100, 1500, 2000, 2500, 3000, 3500, 4500, 5000, etc. Here, the side length refers to the height of the inverted truncated pyramid-shaped groove.
According to the method of the present invention, preferably, the groove of the frame base layer has a side length of 0.1 to 5000 μm, preferably 1 to 1000 μm, and more preferably 2 to 100 μm, when it has a square shape. The side lengths may be, for example: 0.1 μm, 0.2 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 5 μm, 12 μm, 15 μm, 20 μm, 22 μm, 25 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm, 58 μm, 60 μm, 62 μm, 65 μm, 68 μm, 70 μm, or 72 μm, 75 μm, 78 μm, 80 μm, 82 μm, 85 μm, 88 μm, 90 μm, 92 μm, 95 μm, 98 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, 160 μm, 165 μm, 170 μm, 175 μm, 180 μm 185 μm, 190 μm, 195 μm, 200 μm, 210 μm, 230 μm, 250 μm, 280 μm, 300 μm, 310 μm, 330 μm, 350 μm, 380 μm, 400 μm, 410 μm, 430 μm, 450 μm, 480 μm, 500 μm, 510 μm, 530 μm, 550 μm, 580 μm, 600 μm, 610 μm, 630 μm, 650 μm, 680 μm, 700 μm, 710 μm, 730 μm, 750 μm, 780 μm, 800 μm, 810 μm, 830 μm, 850 μm, 880 μm, 900 μm, 910 μm, 930 μm, 950 μm, 980 μm, 1000 μm, 1100 μm, 1500 μm, 2000 μm, 2500 μm, 3000 μm, 3500 μm, 4000 μm, 4500 μm, 5000 μm and the like.
According to the method, the frame base layer can be made of hard materials or flexible materials; preferably, the material of the frame base layer is a composite material of any one or more of Si, PDMS (polydimethylsiloxane), PMMA (polymethyl methacrylate), PET (polyethylene terephthalate), al and ceramic.
According to the method of the present invention, preferably, the frame base layer may be formed by one or more of an etching method, a stencil printing method, and a breathing pattern method.
The etching method is a method of performing engraving etching on the surface of a substrate by using a physical or chemical method to pattern the substrate, such as wet etching of a silicon wafer, electron beam etching, focused ion beam lithography, and the like.
The template imprinting method is a technique of transferring a structure on a template to a material to be processed through a material having thermoplasticity or photoplasticity, such as polydimethylsiloxane, photoresist, or the like.
The respiratory pattern method is a micro-nano structure processing method, and is a method for forming a periodic polymer pore structure by utilizing a liquid drop array formed by condensing water vapor or other steam on the surface of a polymer solution and sequentially volatilizing a polymer solvent and liquid drops.
Specific conditions of the etching method, the template imprinting method, and the breathing pattern method are not particularly limited, and those skilled in the art may specifically select the etching method, the template imprinting method, and the breathing pattern method according to a desired framework base structure.
According to the method of the present invention, preferably, the structured color layer has a reflection peak position of the structured color of 200 to 2000nm, preferably 310 to 1050nm, more preferably 390 to 780nm.
According to the method, the micro-nano structure of the structural color layer comprises one or more of a film, a grating, a super surface, a photonic crystal, an amorphous photonic structure, a disordered structure and a composite structure.
Preferably, the film comprises a film formed of a transparent solid, a film formed of a liquid, a thin layer of a gas sandwiched by two pieces of glass, or a multilayer film in which multilayer interference can occur.
Preferably, the grating comprises a one-dimensional grating and/or a two-dimensional grating.
Preferably, the super-surface comprises one or more of a metal optical super-surface, a metal oxide super-surface, a nitride super-surface and a high refractive index material super-surface.
The metal oxide super surface may be, for example, tiO 2 Super-surface, etc.
The nitride super-surface may be, for example, a TiN super-surface.
The high refractive index material super-surface may be, for example, a silicon super-surface.
Preferably, the photonic crystal comprises one or more of a one-dimensional photonic crystal, a two-dimensional photonic crystal and a three-dimensional photonic crystal.
In the invention, the one-dimensional photonic crystal refers to a multilayer film which has dielectric constant periodic arrangement in one direction and mainly comprises different medium periodic arrangement components. For example, the film can be prepared by any one of an alternating coating method, a spin coating method, a spray coating method, a pulling method, an LB film technology, a layer-by-layer stacking technology, electron beam exposure, two-photon polymerization and 3D printing.
The two-dimensional photonic crystal is formed by periodically arranging dielectric constants in two directions and mainly comprises a grating structure with characteristic dimension of wavelength magnitude, a two-dimensional lattice structure and the like. For example, it can be produced by any of a self-assembly method, an etching method, a multi-beam interference method, two-photon polymerization, and 3D printing.
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 and the like. For example, the optical film can be prepared by any one of a self-assembly method, a layer-by-layer stacking technique, a holographic lithography method, a sacrificial template method, two-photon polymerization, and 3D printing.
Preferably, the amorphous photonic structure is a short-range ordered long-range disordered quasiperiodic structure. For example, spongy structures in parrot feathers (PNAS 2012 109 (27) 10798-10801), spongy structures in Nitraria Cotinga maynana hairs (Soft Matter,2009,5, 1792-1795), and fibrous structures of proteins in The same thickness, at equal distances and in parallel in The facial skin of Nitraria glauca (The Journal of Experimental Biology 207, 2157-2172).
Preferably, the structural color generated by the disordered structure scattering is Rayleigh scattering and Mie scattering, for example, blue on a dragonfly body is also derived from the uncorrelated scattering of light by scattering particles in the body.
Preferably, the composite structure is produced by utilizing the composite action of a plurality of structures, and multifunctional structural colors with iridescence effect, polarization effect, high saturation and high brightness can be realized.
According to the present invention, preferably, the method further comprises the step of forming a transparent material layer on the structural color layer.
Preferably, the transparent material used for forming the transparent material layer is one or more of silk fibroin, cellulose, starch, polyimide, epoxy resin, light-cured glue, varnish, PMMA, PDMS and PET.
Further, the transparent material layer may be formed by spin coating, doctor coating, drop coating, spray coating, or the like.
The thickness of the transparent material layer may be sufficient to make the surface of the obtained structural color film with high mechanical stability flat.
According to the third aspect of the invention, the high-mechanical-stability structural color film prepared by the preparation method of the high-mechanical-stability structural color film is provided.
According to the fourth aspect of the invention, the high mechanical stability structural color film or the high mechanical stability structural color film prepared by the preparation method of the high mechanical stability structural color film is applied to wearable, display, package decoration, sensing and anti-counterfeiting.
The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.
Example 1
(1) A grating sheet of 10 × 5cm was cut, cleaned and placed in a petri dish, and a PDMS prepolymer (available from dow corning, model number Sylgard 184) was prepared by mixing component a and component B in a weight ratio of 10:1, uniformly mixing and fully stirring, and then putting the mixture into a centrifuge for 5min at a speed of 3000r/min to remove bubbles generated in the mixing process. And casting the prepared PDMS on the surface of the grating sheet, 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 2h. After cooling to room temperature, the PDMS is peeled off from the grating sheet lightly, and the PDMS film with the groove-shaped structure is obtained.
(2) Fully and ultrasonically treating a 28 mass percent monodisperse polystyrene microsphere solution with the particle size of 210nm to uniformly disperse the solution;
fixing a PDMS film on a platform of an automatic film coating machine, using a liquid transfer gun to transfer 50 mu L (2) of polystyrene globule solution, dropwise adding the polystyrene globule solution on the surface of the PDMS film, setting the blade coating speed to be 100mm/s and the blade coating length to be 120mm, enabling a wire rod of the automatic film coating machine to scrape the surface of the PDMS film to form a liquid film, and naturally drying at room temperature;
(3) And (3) annealing the PDMS film coated with the colloid photonic crystals in an oven at 80 ℃ for 1 hour to firmly combine the small balls and the PDMS film, thus obtaining the structural color film with high mechanical stability.
FIG. 1 is an SEM image of a structural color film with high mechanical stability having a trench-like structure with a plurality of trenches filled with optical crystals obtained in example 1, wherein the frame structure is a trench-like structure with a period of 160 μm and a depth of 40 μm. Fig. 2 is a SEM cross-sectional view of a trench structure assembled with a photonic crystal, wherein 1 is a photonic crystal (structural color layer) filled in the trench frame structure, and 2 is the trench frame structure, and it can be seen from the figure that the colloidal beads are assembled in the trench, and the shape of the trench protects the photonic crystal structure inside the trench.
Fig. 3 is a comparison of structural colors of the structural color film prepared in example 1 before and after rubbing, and it can be seen from fig. 5 that the structural color was not affected after 10 times of rubbing with a finger and 10 times of rubbing with a doctor blade.
Example 2
(1) Taking a proper amount of silicon dioxide pellets with the diameter of 10 mu m on a flat PDMS (polydimethylsiloxane) substrate, lightly pressing the silicon dioxide powder by using another PDMS sheet, and performing one-way friction to obtain a single-layer compact silicon dioxide pellet layer.
(2) The PDMS substrate processed above is cut to a suitable size, placed in a KW-4A type spin coater, 50 μ L of photo-curable ink (China academy of sciences chemical research institute, green printing focus laboratory type R-03C) is spin-coated on the single-layer silica beads at a speed of 300rpm for 20s, and the above steps are repeated twice. After the solvent is completely volatilized, the solution is irradiated and cured for 3min under an ultraviolet lamp.
(3) And (3) taking 10g of prepared PDMS, and pouring the PDMS on the template in the step (2). Placing in a sealed vacuum box for 20min to remove air bubbles. The sample was taken out and placed in an oven at 80 ℃ for 2h. And taking out the sample, and slightly stripping the PDMS soft template to obtain the frame structure.
(4) And (2) carrying out ultrasonic treatment on 0.5% of polystyrene small ball (particle size is 230 nm) emulsion (solvent is a mixed solvent of water and absolute ethyl alcohol in a volume ratio of 1.
20 μ L of polystyrene emulsion was dropped onto the surface of the frame structure. And assembling the photonic crystal at a blade coating speed of 0.1mm/s and a hot stage temperature of 60 ℃ to obtain the structural color film with high mechanical stability.
Fig. 4 is an optical microscope photograph of the high mechanical stability structure color thin film having a hemispherical groove structure with a plurality of hemispherical grooves and optical crystals assembled therein obtained in example 2, and it can be seen from fig. 4 that the thin film has a plurality of hemispherical groove structures. Fig. 5 is an SEM image of the hemispherical structure with the photonic crystal assembled therein in fig. 4, in which 1 is a photonic crystal (structural color layer) filled in the hemispherical structure, and 2 is a hemispherical frame structure. As can be seen from fig. 5, the presence of the hemispherical frame structure provides a protective effect for the structural color layer therein.
The abrasion resistance was measured by the same method as in example 1, and the structural color was not affected as well.
Example 3
(1) And (3) placing the Si sheet with the mask plate in a TMAH (tetramethylammonium hydroxide) 25% aqueous solution, and etching for 10min. Taking out ions for cleaning, and drying the surface by using nitrogen.
(2) And (3) taking 10g of prepared PDMS, and pouring the PDMS on the template in the step (1). Placing in a sealed vacuum box for 20min to remove air bubbles. The sample was taken out and placed in an oven at 80 ℃ for 2h. And taking out the sample, and slightly stripping the PDMS soft template to obtain the reverse frame structure.
(3) And (3) taking 10g of prepared PDMS, and pouring the PDMS on the inverted frame structure template in the step (2). And (3) repeating the step (2) to obtain the PDMS framework structure.
(4) A proper amount of polystyrene bead emulsion with the mass fraction of 10% and the particle size of 230nm is taken to be arranged on a frame structure, a glass cover plate with the surface hydrophobized is covered on the frame structure, the height of a limited domain is 40 mu m, a photonic crystal film is prepared, after the solution is volatilized, a structural color film with high mechanical stability is obtained, and a scanning electron microscope picture shows that the colloidal beads are assembled in the grooves in the shape of the inverted truncated pyramid to form a three-dimensional photonic crystal structure.
The abrasion resistance was measured by the same method as in example 1, and the structural color was not affected as a result.
Example 4
(1) And (3) placing the Si sheet with the mask plate in 25 mass% aqueous solution of TMAH (tetramethylammonium hydroxide), and etching for 10min. Taking out ions, cleaning and drying the surface by nitrogen.
(2) And (3) taking 10g of prepared PDMS, and pouring the PDMS on the template in the step (1). Placing in a sealed vacuum box for 20min to remove air bubbles. The sample was taken out and placed in an oven at 80 ℃ for 2h. And taking out the sample, and slightly stripping the PDMS soft template to obtain the reverse frame structure.
(3) And (3) taking 10g of prepared PDMS, and pouring the PDMS on the reverse frame structure template in the step (2). And (3) repeating the step (2) to obtain the PDMS framework structure.
(4) 5 percent of polystyrene microsphere emulsion with the particle size of 600nm by mass percent 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.
(5) Cutting a 5cm multiplied by 8cm PDMS frame film, cleaning and carrying out hydrophilic treatment, and assembling a two-dimensional photonic crystal on the surface of the PDMS frame film by using an interface self-assembly method, wherein the specific operation is as follows: putting a PET film into a glass culture dish, pouring pure water to enable the water surface to be submerged in the PET film, sucking a proper amount of polystyrene pellet mixed solution by a liquid transfer gun and dripping the mixed solution on the liquid surface, dripping a plurality of drops of sodium dodecyl sulfate solution on the edge of the glass culture dish when the pellets are fully paved on the whole liquid surface, assembling the polystyrene pellets into a highly ordered two-dimensional photonic crystal at a gas-liquid interface, transferring the orderly arranged polystyrene pellet close-packed film to the surface of a PDMS frame film by a film fishing method, and annealing at 80 ℃ for 1 hour to enable the pellets to be firmly combined with the PDMS frame film substrate, thereby obtaining the structural color film with high mechanical stability. According to a scanning electron microscope image, the colloid balls are assembled in the grooves in the shape of the inverted truncated pyramid to form a two-dimensional photonic crystal structure.
The abrasion resistance was measured by the same method as in example 1, and the structural color was not affected as a result.
Example 5
(1) And (3) taking a proper amount of silicon dioxide pellets with the diameter of 10 mu m on a flat PDMS substrate, lightly pressing the silicon dioxide pellets on silicon dioxide powder by using another PDMS sheet, and performing one-way friction to obtain a single-layer compact silicon dioxide layer.
(2) The PDMS substrate processed above is cut to a suitable size, placed in a KW-4A type spin coater, 50 μ L of photo-curable ink (China academy of sciences chemical research institute, green printing focus laboratory type R-03C) is spin-coated on the single-layer silica beads at a speed of 300rpm for 20s, and the above steps are repeated twice. After the solvent is completely volatilized, the solution is irradiated and cured for 3min under an ultraviolet lamp.
(3) And (3) taking 10g of prepared PDMS, and pouring the PDMS on the template in the step (2). Placing in a sealed vacuum box for 20min to remove air bubbles. The sample was taken out and placed in an oven at 80 ℃ for 2h. And taking out the sample, and slightly stripping the PDMS soft template to obtain the frame structure.
(4) 20 mu L of polystyrene microsphere emulsion with the mass fraction of 10% and the particle size of 230nm is put on a frame structure, a surface clean glass cover is covered on the frame structure, a photonic crystal film (the height of a limited domain is 40 mu m) is prepared by a limited domain method, and a structural color film with high mechanical stability is obtained after the solution is volatilized. According to a scanning electron microscope image, the colloid balls are assembled in the hemispherical grooves to form a three-dimensional photonic crystal structure.
The abrasion resistance was measured by the same method as in example 1, and the structural color was not affected as well.
Example 6
A structural color film of high mechanical stability was prepared as in example 1, except that 200. Mu.L of the prepared PDMS solution was pipetted using a pipette, the pipetted PDMS solution was spin-coated on the structural color layer of high mechanical stability using a KW-4A type spin coater, and the coating was maintained at low speed (500 r/min) for 5 seconds; the temperature was maintained at high speed (5000 r/min) for 30 seconds.
Putting the film into a vacuum drier, vacuumizing for 2min, taking out a sample, and putting the sample into an oven with the temperature of 80 ℃ for heating for 1h to obtain the structural color film with high mechanical stability.
The abrasion resistance was measured by the same method as in example 1, and the structural color was not affected as well.
Example 7
A structural color film of high mechanical stability was prepared by following the procedure of example 1 except that a solution of PMMA was spin-coated on a single layer of silica spheres in step (2). And after the solution is completely volatilized, obtaining the structural color film with high mechanical stability.
The abrasion resistance was measured by the same method as in example 1, and the structural color was not affected as well.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, 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 the combination of specific features in any suitable manner, the invention is not described in detail in order to avoid unnecessary repetition. Such simple modifications and combinations should be considered within the scope of the present disclosure as well.
Claims (10)
1. A high mechanical stability structural color film, characterized in that the film comprises a frame base layer and a structural color layer, wherein the frame base layer is provided with more than one groove, and the structural color layer is formed in the groove; the structure color layer is provided with a micro-nano structure, and the micro-nano structure can interact with light to generate a structure color.
2. The film of claim 1, wherein the groove of the frame substrate is one or more of a groove shape, a hemispherical shape, a bowl shape, an inverted pyramid shape, an inverted triangular pyramid shape, an inverted frustum shape, and a square shape;
preferably, when the groove of the frame base layer is groove-shaped, the depth is 0.1-5000 μm, preferably 1-1000 μm, and more preferably 2-100 μm;
preferably, when the groove of the frame base layer is hemispherical, the diameter thereof is 0.1-5000 μm, preferably 1-1000 μm, and more preferably 2-100 μm;
preferably, the groove of the frame base layer is bowl-shaped, and the diameter of the groove is 0.1-5000 μm, preferably 1-1000 μm, and more preferably 2-100 μm;
preferably, when the groove of the frame base layer is in an inverted pyramid shape, the side length is 0.1-5000 μm, preferably 1-1000 μm, and more preferably 2-100 μm;
preferably, when the groove of the frame base layer is in the shape of an inverted frustum of a pyramid, the side length of the groove is 0.1-5000 μm, preferably 1-1000 μm, and more preferably 2-100 μm;
preferably, the groove of the frame base layer has a side length of 0.1 to 5000 μm, preferably 1 to 1000 μm, and more preferably 2 to 100 μm, when it has a square shape.
3. The film according to claim 1 or 2, wherein the frame base layer is made of hard material or flexible material;
preferably, the material of the frame base layer is a composite material of any one or more of Si, PDMS, PMMA, PET, al and ceramic;
preferably, the frame base layer is formed by one or more of an etching method, a stencil printing method, and a breathing pattern method.
4. A film according to any one of claims 1 to 3, wherein the structured color layer has a reflection peak position of 200 to 2000nm, preferably 310 to 1050nm, more preferably 390 to 780nm;
the micro-nano structure of the structural color layer comprises one or more of a film, a grating, a super surface, a photonic crystal, an amorphous photonic structure, a disordered structure and a composite structure;
preferably, the thin film can generate structural color by interference, and the thin film comprises a thin film formed by transparent solid, a thin film formed by liquid, a thin gas layer sandwiched by two pieces of glass or a multilayer film capable of generating multilayer interference;
preferably, the grating comprises a one-dimensional grating and/or a two-dimensional grating;
preferably, the super-surface comprises one or more of a metal optical super-surface, a metal oxide optical super-surface, a nitride optical super-surface, and a high refractive index material super-surface;
preferably, the photonic crystal comprises one or more of a one-dimensional photonic crystal, a two-dimensional photonic crystal and a three-dimensional photonic crystal;
preferably, the one-dimensional photonic crystal is prepared by any one of an alternate coating method, a spin coating method, a spraying method, a pulling method, an LB film technology, a layer-by-layer stacking technology, electron beam exposure, two-photon polymerization and 3D printing;
preferably, the two-dimensional photonic crystal is prepared by any one of a self-assembly method, an etching method, a multi-beam interference method, two-photon polymerization, and 3D printing;
preferably, the three-dimensional photonic crystal is prepared by any one of a self-assembly method, a layer-by-layer stacking technology, a holographic lithography method, a sacrificial template method, two-photon polymerization and 3D printing;
preferably, the amorphous photonic structure is a short-range ordered long-range disordered quasiperiodic structure;
preferably, the structural color generated by the disordered structure scattering is Rayleigh scattering and Mie scattering;
preferably, the composite structure is a multifunctional structural color which is generated by utilizing the composite action of a plurality of structures and can realize iridescence effect, polarization effect, high saturation and high brightness;
preferably, the structural colour layer is covered with a layer of transparent material;
preferably, the transparent material in the transparent material layer is one or more of silk fibroin, cellulose, starch, polyimide, epoxy resin, light-cured glue, varnish, PMMA, PDMS and PET.
5. A method for preparing a structural color film with high mechanical stability is characterized by comprising the following steps,
1) A step of preparing a frame base layer having one or more grooves;
2) A step of forming a structural color layer in the groove,
the structure color layer is provided with a micro-nano structure, and the micro-nano structure can interact with light to generate a structure color.
6. The method of claim 5, wherein the groove of the frame substrate is one or more of a groove shape, a hemispherical shape, a bowl shape, an inverted pyramid shape, an inverted triangular pyramid shape, an inverted frustum shape, and a square shape;
preferably, when the groove of the frame base layer is groove-shaped, the depth is 0.1-5000 μm, preferably 1-1000 μm, and more preferably 2-100 μm;
preferably, when the groove of the frame base layer is hemispherical, the diameter thereof is 0.1-5000 μm, preferably 1-1000 μm, and more preferably 2-100 μm;
preferably, the groove of the frame base layer is bowl-shaped, and the diameter of the groove is 0.1-5000 μm, preferably 1-1000 μm, and more preferably 2-100 μm;
preferably, when the groove of the frame base layer is in an inverted pyramid shape, the side length is 0.1-5000 μm, preferably 1-1000 μm, and more preferably 2-100 μm;
preferably, when the groove of the frame base layer is in the shape of an inverted frustum of a pyramid, the side length of the groove is 0.1-5000 μm, preferably 1-1000 μm, and more preferably 2-100 μm;
preferably, the groove of the frame base layer has a side length of 0.1 to 5000 μm, preferably 1 to 1000 μm, and more preferably 2 to 100 μm, when it has a square shape.
7. The method according to claim 5 or 6, wherein the frame substrate is made of hard material or flexible material;
preferably, the material of the frame base layer is a composite material of any one or more of Si, PDMS, PMMA, PET, al and ceramic;
preferably, the frame base layer is formed by one or more of an etching method, a stencil printing method, and a respiratory pattern method.
8. The method according to any one of claims 5 to 7, wherein the structured color layer has a reflection peak position of 200 to 2000nm, preferably 310 to 1050nm, more preferably 390 to 780nm;
the micro-nano structure of the structural color layer comprises one or more of a film, a grating, a super surface, a photonic crystal, an amorphous photonic structure, a disordered structure and a composite structure;
preferably, the film can generate structural color by interference, and the film comprises a film formed by transparent solid, a film formed by liquid, a gas thin layer sandwiched by two pieces of glass, or a multilayer film capable of generating multilayer interference;
preferably, the grating comprises a one-dimensional grating and/or a two-dimensional grating;
preferably, the super-surface comprises one or more of a metal optical super-surface, a metal oxide super-surface, a nitride super-surface and a high refractive index material super-surface;
preferably, the photonic crystal comprises one or more of a one-dimensional photonic crystal, a two-dimensional photonic crystal and a three-dimensional photonic crystal;
preferably, the one-dimensional photonic crystal is prepared by any one of an alternate coating method, a spin coating method, a spraying method, a pulling method, an LB film technology, a layer-by-layer stacking technology, electron beam exposure, two-photon polymerization and 3D printing;
preferably, the two-dimensional photonic crystal is prepared by any one of a self-assembly method, an etching method, a multi-beam interference method, two-photon polymerization and 3D printing;
preferably, the three-dimensional photonic crystal is prepared by any one of a self-assembly method, a layer-by-layer stacking technology, a holographic lithography method, a sacrificial template method, two-photon polymerization and 3D printing;
preferably, the amorphous photonic structure is a short-range ordered long-range disordered quasiperiodic structure;
preferably, the structural color generated by the disordered structure scattering is Rayleigh scattering and Mie scattering;
preferably, the composite structure is a multifunctional structural color which is generated by utilizing the composite action of a plurality of structures and can realize iridescence effect, polarization effect, high saturation and high brightness;
preferably, the method further comprises the step of forming a layer of transparent material on the structural color layer;
preferably, the transparent material used for forming the transparent material layer is one or more of silk fibroin, cellulose, starch, polyimide, epoxy resin, light-cured glue, varnish, PMMA, PDMS and PET.
9. The high mechanical stability structural color film prepared by the method for preparing the high mechanical stability structural color film according to any one of claims 5 to 8.
10. Use of the high mechanical stability structured color film of any one of claims 1 to 4 and 5 or the high mechanical stability structured color film of any one of claims 5 to 8 in wearable, display, packaging decoration, sensing and anti-counterfeiting applications.
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| CN202110537315 | 2021-05-18 | ||
| CN202110537315X | 2021-05-18 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116203655A (en) * | 2023-05-04 | 2023-06-02 | 北京理工大学 | Sodium-based heat-sensitive optical super-surface and heat-sensitive structural device with optical super-surface |
| CN116200125A (en) * | 2023-02-01 | 2023-06-02 | 广东安捷伦新材料科技有限公司 | Film nano-structure color paint |
-
2022
- 2022-03-22 CN CN202210285633.6A patent/CN115373057A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116200125A (en) * | 2023-02-01 | 2023-06-02 | 广东安捷伦新材料科技有限公司 | Film nano-structure color paint |
| CN116203655A (en) * | 2023-05-04 | 2023-06-02 | 北京理工大学 | Sodium-based heat-sensitive optical super-surface and heat-sensitive structural device with optical super-surface |
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