CN113990844A - Preparation method of anti-counterfeit label based on multilayer quasi-amorphous photon heterostructure - Google Patents
Preparation method of anti-counterfeit label based on multilayer quasi-amorphous photon heterostructure Download PDFInfo
- Publication number
- CN113990844A CN113990844A CN202111251657.1A CN202111251657A CN113990844A CN 113990844 A CN113990844 A CN 113990844A CN 202111251657 A CN202111251657 A CN 202111251657A CN 113990844 A CN113990844 A CN 113990844A
- Authority
- CN
- China
- Prior art keywords
- sio
- layer
- quasi
- spraying
- multilayer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 119
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 119
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 119
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 119
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 119
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 115
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000002245 particle Substances 0.000 claims abstract description 61
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 57
- 238000005507 spraying Methods 0.000 claims abstract description 54
- 239000010410 layer Substances 0.000 claims abstract description 50
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002096 quantum dot Substances 0.000 claims abstract description 17
- 239000011247 coating layer Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 48
- 239000011248 coating agent Substances 0.000 claims description 33
- 238000000576 coating method Methods 0.000 claims description 33
- 239000000084 colloidal system Substances 0.000 claims description 14
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 14
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 14
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims description 14
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims description 14
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 239000004038 photonic crystal Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000149 argon plasma sintering Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000000149 penetrating effect Effects 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 19
- 239000002131 composite material Substances 0.000 description 11
- 238000010586 diagram Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/544—Marks applied to semiconductor devices or parts, e.g. registration marks, alignment structures, wafer maps
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2223/00—Details relating to semiconductor or other solid state devices covered by the group H01L23/00
- H01L2223/544—Marks applied to semiconductor devices or parts
- H01L2223/54413—Marks applied to semiconductor devices or parts comprising digital information, e.g. bar codes, data matrix
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2223/00—Details relating to semiconductor or other solid state devices covered by the group H01L23/00
- H01L2223/544—Marks applied to semiconductor devices or parts
- H01L2223/54433—Marks applied to semiconductor devices or parts containing identification or tracking information
- H01L2223/5444—Marks applied to semiconductor devices or parts containing identification or tracking information for electrical read out
Landscapes
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a preparation method of an anti-counterfeit label based on a multilayer quasi-amorphous photon heterostructure. The multilayer structure is prepared by spraying SiO with rapid spraying method2And Fe3O4@SiO2The colloidal particle ethanol solution is sprayed on the substrate alternately. Meanwhile, in order to obtain the encrypted information of ultraviolet response, a small amount of quantum dots are doped in the spraying process. When a solvent such as ethanol is permeated into the coating layer, the solvent and SiO2Refractive index of close, SiO2The layer becomes transparent, and Fe3O4@SiO2In the layer due to Fe3O4The high refractive index difference with the solvent allows the structural color information carried by the layer to be fully displayed. After the solvent is volatilized, SiO2The intense scattering of incident light by the layer results in the layer being opaque, Fe3O4@SiO2The information of the layer is re-hidden. In addition, Fe3O4@SiO2The fluorescence information carried by the quantum dots in the layer can be made to fluoresce while the solvent is appliedThe environment is further displayed. The novel and flexible information encryption/decryption mode and the simple and fast manufacturing process make the anti-counterfeiting and multi-information encryption system have wide application prospect in the fields of anti-counterfeiting and multi-information encryption.
Description
Technical Field
The invention belongs to the technical field of information encryption/anti-counterfeiting materials, and particularly relates to a preparation method of an anti-counterfeiting label based on a multilayer quasi-amorphous photon heterostructure.
Background
Currently, with the advent of many high resolution scanning, detection, replication, and counterfeiting technologies, merchandise counterfeiting has become a global problem, posing serious threats and negative impacts to individuals, businesses, and society. The development of more novel and reliable information encryption and anti-counterfeiting technologies is a subject to be urgently solved. Over the past decades, various anti-counterfeiting strategies have been proposed for merchandise, including fingerprints, watermarks, holographic patterns, fluorescent labels, plasma labels, and structural color patterns. Among them, the response type photon material with visible structural color has attracted wide attention in the fields of information encryption and anti-counterfeiting due to its unique optical characteristics and various stimulus response modes. To date, various stimulus-responsive photonic crystal anti-counterfeiting strategies have been developed, including solvent response, mechanical stretching drive, vapor adsorption induction, thermal excitation, magnetic field stimulation, optical switching, and the like. Among them, the use of solvents to implement structural color switching to implement encryption and decryption of information has attracted great interest due to its unique working method. However, the anti-counterfeiting strategy based on structural color solvent response is mainly focused on long-range ordered photonic crystals at present. The long-range ordered structure has low preparation efficiency, complex process and high cost, and the structure color angle dependence phenomenon can increase the difficulty of information decryption under certain conditions. On the contrary, the colloidal particle array with the short-range order or the quasi-amorphous structure is not only easy to prepare, but also the non-rainbow structural color of the colloidal particle array is helpful to improve the reliability of information decryption. In order to achieve solvent response of structural colors using quasi-amorphous photonic structures, it is currently common to use hollow SiO2And PS and other colloid particles to constitute short-range ordered colloid array, and utilizing the refraction of air and solvent inside hollow particleThe difference ensures the presence of structural color. However, it is difficult to form a high refractive index difference between the hollow particles and the solvent, resulting in low structural color brightness and contrast due to the solvent.
Disclosure of Invention
In order to achieve the design goal, the invention provides a preparation method of an anti-counterfeiting label based on a multilayer quasi-amorphous photon heterostructure. The multilayer structure is prepared by spraying SiO with rapid spraying method2And Fe3O4@SiO2The colloidal particle ethanol solution is sprayed on the substrate alternately. In the spraying process, a required encrypted information layer is prepared by using a hollow mask, and meanwhile, a small amount of quantum dots are doped in the spraying process in order to obtain ultraviolet light response encrypted pattern information. Due to SiO2Has a refractive index close to that of ethanol and good affinity, and when the ethanol solvent contacts SiO2When coating, it will penetrate into SiO2In the pores of the colloid array, SiO is added2The coating becomes almost transparent, while Fe3O4@SiO2In the layer due to Fe3O4The high refractive index difference with the solvent allows the structural color information carried by the layer to be fully displayed. When the ethanol is volatilized, SiO2The intense scattering of incident light by the layer results in the layer being opaque, Fe3O4@SiO2The information of the layer is re-hidden. In addition, Fe3O4@SiO2The fluorescence information carried by the quantum dots in the layer can be further displayed in a fluorescent environment while the solvent is applied. The novel and flexible information encryption/decryption mode and the simple and fast manufacturing process make the anti-counterfeiting and multi-information encryption system have wide application prospect in the fields of anti-counterfeiting and multi-information encryption.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing an anti-counterfeit label based on a multilayer quasi-amorphous photon heterostructure uses a spraying method to alternately spray SiO on a substrate2And Fe3O4@SiO2Colloidal particle ethanol solution to form a quasi-amorphous photonic crystal coating, wherein SiO is2For information-shielding layers, Fe3O4@SiO2The layer is a display layer, a hollow mask plate is placed on the substrate when the encrypted pattern is prepared, and Fe3O4@SiO2Continuously spraying a small amount of quantum dots on the layer to form a fluorescent information layer, and determining the working mode of spraying SiO according to the encrypted coating to be prepared2And Fe3O4@SiO2And finally obtaining the multilayer quasi-amorphous photon heterostructure by the sequence of the solution, wherein the steps are as follows:
step one, preparing colloidal particles: by hydrothermal method and
method of separately preparing monodisperse Fe3O4@SiO2And SiO2Colloidal particles of which Fe3O4@SiO2And SiO2The size of the colloid particles is regulated and controlled by changing the adding amount of TEOS in the reaction process, and SiO is generated along with the increase of TEOS amount in the reaction system2Colloidal particle size and Fe3O4Surface SiO2The thickness of the coating layer is gradually increased, SiO2The grain diameter of the colloid particle is 250 nm-280 nm, Fe3O4@SiO2The particle size of the colloid particles is 230 nm-440 nm;
step two, preparing a solution: preparing SiO with the concentration of 5-10 wt%2Ethanol solution and Fe3O4@SiO2Preparing a PDMS precursor solution, and stirring and mixing the PDMS precursor basic components and the curing agent according to the mass ratio of 10: 1;
step three, preparing a PDMS flexible substrate: pouring the prepared PDMS precursor solution in the second step onto the upper surface of a glass substrate for natural leveling, standing for 8-15 minutes, heating to 45-65 ℃ after bubbles are completely eliminated, curing for 3-4 hours, and uncovering a film for later use after curing;
fourthly, preparing a multi-response information encryption coating by a spraying method: respectively spraying the prepared SiO in the second step on the substrate by using a spray gun2Ethanol solution and Fe3O4@SiO2Ethanol solution, placing a hollowed mask on the substrate when preparing the encrypted pattern, and placing Fe3O4@SiO2And continuously spraying a small amount of quantum dots on the layer to form a fluorescent information layer, and finally obtaining the multilayer quasi-amorphous photon heterostructure.
The SiO2The colloid particles are replaced by colloid particles of PMMA and PS with the refractive index similar to that of ethanol.
Fe3O4@SiO2ZrO-containing for colloidal particles2(2.13)、CeO2(2.20)、ZnS(2.35)、TiO2(2.49) or Fe2O3(2.9) high refractive index colloidal particles.
SiO2Adding 2 wt% PVA solution into ethanol solution to strengthen SiO2The adhesion of the particles to the substrate improves the structural stability, and the solvent can be replaced by ethanol/water mixed solution, water, ethanol/ethylene glycol, ethanol/propylene carbonate or silicone oil besides ethanol.
The substrate is a solid substrate with stable physicochemical properties, such as a glass substrate, an aluminum substrate, a PET plastic substrate, a PDMS substrate or paper.
The spray gun uses compressed air or inert gas, and the spraying adopts manual spraying or automatic mechanical spraying, namely SiO2The thickness of the back bottom layer is 8-20 microns, and SiO is2Thickness of the structural color layer is 1-5 microns, Fe3O4@SiO2The thickness of the layer is 1-5 microns, and the temperature of the substrate is controlled to be 50-80 ℃ during spraying.
And (3) using a hollowed mask in the spraying process, and doping quantum dots in the liquid of the partial encrypted pattern to obtain the required encrypted information coating.
The solvents for realizing the display of the encrypted information are ethanol, silicon oil and SiO2The information is shown by penetrating the solvent into the gap of the multilayer quasi-amorphous photon heterostructure and utilizing ethanol and SiO2The close refractive index property reduces light scattering and makes SiO2The layer is transparent and Fe3O4@SiO2Has high refractive index, has large refractive index contrast with alcohol, and thus exhibits bright structural color, and SiO is volatilized2The layer is gradually restored to the original opaque state, and the encrypted information is hidden againAnother switch for the presentation of encrypted information is UV, and information encrypted using quantum dots is only on SiO2The layer is transparent and can be clearly shown in the UV light environment, and the information is invisible in the ambient light.
The solvents for realizing the display of the encrypted information are ethanol, silicon oil and SiO2The information is displayed by penetrating the solvent into the gaps of the multilayer quasi-amorphous photon heterostructure and utilizing the solvent and SiO2The close refractive index property reduces light scattering and makes SiO2The layer is transparent and Fe3O4@SiO2Has a high refractive index and still has a large refractive index contrast with a solvent, thereby exhibiting a bright structural color. With the volatilization of the solvent, SiO2The layer gradually returns to the original opaque state and the encrypted information is again hidden. Another switch for the presentation of encrypted information is UV, where information encrypted using quantum dots is only on SiO2The layer is transparent and can be clearly shown in the UV light environment, and the information is invisible in the ambient light.
The invention has the following beneficial effects:
(1) the preparation method is simple, quick in response and convenient and fast to operate: the spraying method used in the invention is rapid, simple and convenient, and has no special requirements on the substrate. SiO 22The anti-blocking agent has good compatibility with solvents such as ethanol, and the encrypted information can be instantly displayed when the ethanol solvent is dripped; the information encrypted by the quantum dots is displayed instantly only by UV irradiation, and the response speed is high.
(2) The prepared composite film has good safety coefficient and optical performance: only ethanol, silicone oil and the like are mixed with SiO2The structural color information can be displayed only by specific solvents with good chemical affinity and similar refractive indexes. Furthermore, fluorescence information can only be generated when the solvent and the UV light are applied simultaneously. In addition, the unique spectral shift of each structural color information also increases the difficulty of counterfeiting the information. The quasi-amorphous structure photonic crystal composite coating has good optical stability and no angle dependence of structural color, and the encryption/decryption effect is almost unchanged after repeated use.
Drawings
FIG. 1 is a schematic diagram of a method for preparing an anti-counterfeit label with a multilayer quasi-amorphous photon heterostructure by a spraying method.
Fig. 2 is a graph showing the effect of the composite coating layer of the present invention on the appearance/hiding of the encrypted information under the action of ethanol and UV.
FIG. 3 is a spectrum chart of the encrypted information of the composite coating under the action of ethanol and UV in example 1 of the invention.
Fig. 4 is a diagram illustrating the effect of the composite coating layer of embodiment 2 of the present invention in revealing/hiding encrypted information under the effect of ethanol.
Fig. 5 is an effect diagram of switching among various shapes and structural colors of the composite coating under the action of ethanol in embodiment 3 of the present invention.
Fig. 6 is a graph showing the effect of exposing/hiding encrypted information under the action of ethanol in the composite coating on the flexible substrate in example 4 of the present invention.
Fig. 7 is a diagram illustrating the effect of the composite coating layer of embodiment 5 of the present invention in revealing/hiding encrypted information under the effect of ethanol.
Fig. 8 is a graph showing the information anti-counterfeiting effect of the composite coating in embodiment 6 of the present invention under the effect of ethanol.
Fig. 9 is an effect diagram of structural color switching of the composite coating under the action of ethanol in embodiment 7 of the present invention.
Detailed Description
The invention will be further described with reference to specific examples and figures, but the scope of the invention is not limited thereto. Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The invention discloses a preparation method of an anti-counterfeiting label based on a multilayer quasi-amorphous photon heterostructure, and the process is shown in figure 1.
Example 1: a preparation method of an anti-counterfeiting label based on a multilayer quasi-amorphous photon heterostructure specifically comprises the following steps:
i, preparing colloidal particles:
(1)SiO2and (3) preparing colloidal particles. 100ml of absolute ethanol, 7ml of deionized water and 4ml of ammonia (25%) were mixed, stirred for 20 minutes, then 8ml of tetraethyl orthosilicate (TEOS) was injected, and stirring was continued for 5 hours. The waste liquid was then removed by centrifugation and washed three times with water and alcohol, respectively. Drying at 45 deg.C, and collecting.
(2)Fe3O4@SiO2And (3) preparing colloidal particles. First, monodisperse Fe was synthesized by hydrothermal method3O4Colloidal particles. The specific procedure is as follows, 1.35g FeCl is added under magnetic stirring3·6H2O, 2.94g of sodium citrate and 0.9g of urea were dissolved in 80ml of deionized water, and after stirring for 30 minutes, sodium polyacrylate (0.1. mu. mol) was added. After magnetic stirring for 2 hours, the above mixed solution was transferred to a stainless steel autoclave (100ml) having a polytetrafluoroethylene inner container, and then heated at 200 ℃ for 12 hours. Next, the product was magnetically separated and washed several times with water and ethanol, dried at 45 ℃ and collected for use. Then, with the improvement
Method for synthesizing Fe3O4@SiO2Colloidal particles. The specific procedure is as follows, 0.1g Fe3O4Colloidal particles, 12ml of deionized water and 60ml of ethanol were added to a 250ml three-necked flask and sonicated for 30 minutes. Then, a mixed solution of 4ml of ammonia water and 20ml of ethanol was poured into the above mixed solution, and vigorously stirred for 20 minutes to form a uniform alkaline environment. Subsequently, a mixture of 0.3ml TEOS and 10ml ethanol was added dropwise, and stirring was continued at 40 ℃ for 10 hours. Finally, the product was separated magnetically and washed several times with water and ethanol, dried at 45 ℃ and collected for future use. Three particle sizes of Fe3O4@SiO2The amount of TEOS used for the colloidal particles was 0.3ml, 0.4ml and 0.45ml, respectively.
II, preparing a solution:
preparing 8 wt% SiO2Colloidal particle ethanol solution, wherein 2 wt% PVA is added; preparing 8 wt% Fe at the same time3O4@SiO2And (3) carrying out ultrasonic treatment on the colloidal particle ethanol solution for 30 minutes to uniformly disperse the particles.
III, preparing a multilayer quasi-amorphous photon heterostructure by a spraying method:
firstly, the prepared SiO in the second step is sprayed by a spray gun2The liquid was sprayed evenly onto the slide. Then the hollowed-out '123' mask is placed on the sprayed SiO2On the layer, Fe with different grain sizes is sprayed on three numbers of '1' 2 '3' respectively3O4@SiO2. Finally removing the mask and spraying the prepared SiO2The colloidal solution was completely hidden until '123'.
Example 1 in the configuration of Fe3O4@SiO2Colloidal particles in ethanol solution, one of the liquids is mixed with a trace amount of quantum dots, and the liquid is sprayed to the position of the number '3'. The spray gun uses compressed air or inert gas, and manual spraying or automatic mechanical spraying can be adopted during spraying. In the spraying process, the rapid volatilization of the ethanol enables the colloid particles to form an amorphous structure with short-range order and long-range disorder. SiO 22The addition of a small amount of PVA to the solution may improve its adhesion to the substrate. Formed SiO2The thickness of the back bottom layer is 8-20 microns, and Fe3O4@SiO2The thickness of the coating is 1-5 microns. The thickness of the sprayed layer can be regulated by adjusting the spraying times. The temperature of the substrate is controlled at 60 ℃ during spraying.
In example 1, the solvent for realizing the encrypted information display is ethanol, the information display is performed by penetrating the solvent into the gaps of the multilayer quasi-amorphous photonic heterostructure and utilizing the solvent and SiO2The close refractive index property reduces light scattering and makes SiO2The layer is transparent and Fe3O4@SiO2Has a high refractive index and still has a large refractive index contrast with a solvent, thereby exhibiting a bright structural color. With the volatilization of the solvent, SiO2The layer gradually returns to the original opaque state and the encrypted information is again hidden. Another switch for the presentation of encrypted information is UV, where information encrypted using quantum dots is only on SiO2The layer is transparent and can be clearly shown in the UV light environment, and the information is invisible in the ambient light.
The switching effect of the information encryption/decryption state in embodiment 1 is shown in fig. 2. As can be clearly seen in fig. 2, the digital '123' colour pattern is completely hidden when the coating is in the dry state; after alcohol is dripped on the composite coating, the colorful digital '123' pattern is clearly shown; upon application of UV, the quantum dot doped pattern '3' is revealed, and the pattern '12' is hidden. The process can be repeated for many times, and the switching effect is almost unchanged. The reflectance spectra of the numbers in each mode are shown in figure 3.
Example 2: a preparation method of an anti-counterfeiting label based on a multilayer quasi-amorphous photon heterostructure specifically comprises the following steps:
i, preparing colloidal particles:
the procedure is as in example 1, except that Fe of four particle sizes3O4@SiO2The amount of TEOS used for the colloidal particles was 0.3ml, 0.4ml, 0.45ml and 0.5ml, respectively.
II, preparing a solution:
the procedure is as in example 1.
III, preparing a multilayer quasi-amorphous photon heterostructure by a spraying method:
firstly, a hollowed XJTU mask is arranged on a substrate, and Fe with different grain diameters is respectively sprayed on two letters of X' U3O4@SiO2. Then removing the mask and spraying the prepared SiO2The solution was completely hidden until 'X U'. Finally, a hollowed XJTU mask is placed on the prepared coating, and Fe with different grain diameters is sprayed on the J '' -T '' letters3O4@SiO2。
Prepared SiO2The thickness of the coating is 8-20 mu m, and Fe3O4@SiO2The thickness of the coating is 1-3 μm.
The switching effect of the encryption/decryption state in embodiment 2 is shown in fig. 4.
Example 3: a preparation method of an anti-counterfeiting label based on a multilayer quasi-amorphous photon heterostructure specifically comprises the following steps:
i, preparing colloidal particles:
the procedure is as in example 1, exceptCharacterized by SiO of two particle sizes2The amount of TEOS used for the colloidal particles was 7ml and 8ml, respectively.
II, preparing a solution:
the procedure is as in example 1.
III, preparing a multilayer quasi-amorphous photon heterostructure by a spraying method:
firstly, a hollow butterfly mask is arranged on a substrate, and prepared Fe is sprayed3O4@SiO2And (3) solution. Then 'butterfly' is changed into 'petal' mask, and prepared SiO is sprayed2The solution was completely hidden until the 'butterfly' was completely hidden. Finally, the hollow apple mask is placed on the prepared coating, and SiO with another particle size is sprayed2And (3) solution.
Prepared Fe3O4@SiO2The thickness of the coating is 1-3 mu m, and the petal layer is SiO2The thickness of (A) is 8-15 mu m, and the apple is SiO2The thickness of the coating is 1-3 μm.
The switching effect of the encryption/decryption state in embodiment 3 is shown in fig. 5.
Example 4: a preparation method of an anti-counterfeiting label based on a multilayer quasi-amorphous photon heterostructure specifically comprises the following steps:
i, preparing colloidal particles:
the procedure is as in example 2.
II, preparing a solution:
preparing 8 wt% SiO2Adding 2 wt% PVA solution into the ethanol mixed solution; preparing 8 wt% Fe at the same time3O4@SiO2Mixing the ethanol solution, and performing ultrasonic treatment for 30 minutes to uniformly disperse the particles. Preparing a PDMS precursor solution from the basic components and a curing agent according to the mass ratio of 10:1, uniformly stirring, standing for 30 minutes until bubbles are completely eliminated, and using.
III, preparing a PDMS flexible substrate:
pouring the prepared PDMS precursor solution on the upper surface of a glass substrate for natural leveling, standing for 10 minutes, curing for 3 hours at 50 ℃ after bubbles are completely eliminated, and carefully taking the film for later use after curing. The thickness of the film is determined according to the pouring amount of PDMS required to be controlled.
IV, preparing a multilayer quasi-amorphous photon heterostructure by a spraying method:
firstly, a hollowed-out ' 2021 ' mask is placed on a PDMS flexible substrate, and Fe with different particle sizes is respectively sprayed on four numbers of ' 2 ' 0 ' 2 ' 1 ' and3O4@SiO2and (3) solution. Then removing the mask and spraying the prepared SiO2The solution to '2021' was completely hidden.
Fe in example 43O4@SiO2A coating thickness of about 1 to 3 μm, SiO2The thickness of the coating is about 8 to 20 μm.
The switching effect of the encryption/decryption state in embodiment 4 is shown in fig. 6.
Example 5: a preparation method of an anti-counterfeiting label based on a multilayer quasi-amorphous photon heterostructure specifically comprises the following steps:
i, preparing colloidal particles:
the procedure is as in example 2.
II, preparing a solution:
the procedure is as in example 1
III, preparing a multilayer quasi-amorphous photon heterostructure by a spraying method:
firstly spraying prepared Fe3O4@SiO2And (3) solution. Then placing the hollowed-out '2021' mask on the sprayed Fe3O4@SiO2Spraying SiO with different particle sizes on four numbers of ' 2 ' 0 ' 2 ' 1 ' on the coating layer2And (3) solution.
Fe in example 53O4@SiO2A coating thickness of about 1 to 5 μm, SiO2The thickness of the coating is about 1 to 3 μm.
The switching effect of the encryption/decryption state in embodiment 5 is shown in fig. 7.
Example 6: a preparation method of an anti-counterfeiting label based on a multilayer quasi-amorphous photon heterostructure specifically comprises the following steps:
i, preparing colloidal particles:
the procedure is as in example 5, exceptCharacterized by two grain sizes of Fe3O4@SiO2The amount of TEOS used for the colloidal particles was 0.4ml and 0.45ml, respectively.
II, preparing a solution:
the procedure is as in example 1
III, preparing a multilayer quasi-amorphous photon heterostructure by a spraying method:
firstly spraying prepared Fe3O4@SiO2A liquid. Then placing the hollowed XJTU mask on the sprayed Fe3O4@SiO2Spraying SiO with different particle sizes on the three letters of 'X' J 'T' on the upper surface of the coating layer2Spraying prepared Fe with another grain diameter on the 'U' letter3O4@SiO2And (3) solution.
Fe in example 63O4@SiO2A coating thickness of about 1 to 5 μm, SiO2The thickness of the coating is about 1 to 3 μm.
The switching effect of the encryption/decryption state in embodiment 6 is shown in fig. 8.
Example 7: a preparation method of an anti-counterfeiting label based on a multilayer quasi-amorphous photon heterostructure specifically comprises the following steps:
i, preparing colloidal particles:
the procedure is as in example 1.
II, preparing a solution:
the procedure is as in example 1.
Thirdly, preparing a multilayer quasi-amorphous photon heterostructure by a spraying method:
firstly, a hollow butterfly mask is arranged on a substrate, and prepared Fe is sprayed3O4@SiO2Solution and then spraying SiO2And (3) solution.
Fe in example 73O4@SiO2A coating thickness of about 1 to 5 μm, SiO2The thickness of the coating is about 0.5 to 3 μm.
The switching effect of the encryption/decryption states in example 7 is shown in fig. 9 (the color of the butterfly is different in the two states).
The above-mentioned embodiments are merely illustrative of the inventive concept of the present invention, and are not intended to limit the scope of the claims of the present invention.
Claims (8)
1. A preparation method of an anti-counterfeiting label based on a multilayer quasi-amorphous photon heterostructure is characterized by comprising the following steps: alternately spraying SiO on the substrate by using a spraying method2And Fe3O4@SiO2Colloidal particle ethanol solution to form a quasi-amorphous photonic crystal coating, wherein SiO is2For information-shielding layers, Fe3O4@SiO2The layer is a display layer, a hollow mask plate is placed on the substrate when the encrypted pattern is prepared, and Fe3O4@SiO2Continuously spraying a small amount of quantum dots on the layer to form a fluorescent information layer, and determining the working mode of spraying SiO according to the encrypted coating to be prepared2And Fe3O4@SiO2And finally obtaining the multilayer quasi-amorphous photon heterostructure by the sequence of the solution, wherein the steps are as follows:
step one, preparing colloidal particles: by hydrothermal method and
method of separately preparing monodisperse Fe3O4@SiO2And SiO2Colloidal particles of which Fe3O4@SiO2And SiO2The size of the colloid particles is regulated and controlled by changing the adding amount of TEOS in the reaction process, and SiO is generated along with the increase of TEOS amount in the reaction system2Colloidal particle size and Fe3O4Surface SiO2The thickness of the coating layer is gradually increased, SiO2The grain diameter of the colloid particle is 250 nm-280 nm, Fe3O4@SiO2The particle size of the colloid particles is 230 nm-440 nm;
step two, preparing a solution: preparing SiO with the concentration of 5-10 wt%2Ethanol solution and Fe3O4@SiO2Ethanol solution, PDMS precursor basic components and curingThe agents are stirred and mixed according to the mass ratio of 10: 1;
step three, preparing a PDMS flexible substrate: pouring the prepared PDMS precursor solution in the second step onto the upper surface of a glass substrate for natural leveling, standing for 8-15 minutes, heating to 45-65 ℃ after bubbles are completely eliminated, curing for 3-4 hours, and uncovering a film for later use after curing;
fourthly, preparing a multi-response information encryption coating by a spraying method: respectively spraying the prepared SiO in the second step on the substrate by using a spray gun2Ethanol solution and Fe3O4@SiO2Ethanol solution, placing a hollowed mask on the substrate when preparing the encrypted pattern, and placing Fe3O4@SiO2And continuously spraying a small amount of quantum dots on the layer to form a fluorescent information layer, and finally obtaining the multilayer quasi-amorphous photon heterostructure.
2. The preparation method of the anti-counterfeit label based on the multilayer quasi-amorphous photonic heterostructure, according to claim 1, is characterized in that: the SiO2The colloid particles are replaced by colloid particles of PMMA and PS with the refractive index similar to that of ethanol.
3. The preparation method of the anti-counterfeit label based on the multilayer quasi-amorphous photonic heterostructure, according to claim 1, is characterized in that: fe3O4@SiO2ZrO-containing for colloidal particles2(2.13)、CeO2(2.20)、ZnS(2.35)、TiO2(2.49) or Fe2O3(2.9) high refractive index colloidal particles.
4. The preparation method of the anti-counterfeit label based on the multilayer quasi-amorphous photonic heterostructure, according to claim 1, is characterized in that: SiO 22Adding 2 wt% PVA solution into ethanol solution to strengthen SiO2The adhesion of the particles to the substrate improves the structural stability, and the solvent can be replaced by ethanol/water mixed solution, water, ethanol/ethylene glycol, ethanol/propylene carbonate or silicone oil besides ethanol.
5. The preparation method of the anti-counterfeit label based on the multilayer quasi-amorphous photonic heterostructure, according to claim 1, is characterized in that: the substrate is a solid substrate with stable physicochemical properties, such as a glass substrate, an aluminum substrate, a PET plastic substrate, a PDMS substrate or paper.
6. The preparation method of the anti-counterfeit label based on the multilayer quasi-amorphous photonic heterostructure, according to claim 1, is characterized in that: the spray gun uses compressed air or inert gas, and the spraying adopts manual spraying or automatic mechanical spraying, namely SiO2The thickness of the back bottom layer is 8-20 microns, and SiO is2Thickness of the structural color layer is 1-5 microns, Fe3O4@SiO2The thickness of the layer is 1-5 microns, and the temperature of the substrate is controlled to be 50-80 ℃ during spraying.
7. The preparation method of the anti-counterfeit label based on the multilayer quasi-amorphous photonic heterostructure, according to claim 1, is characterized in that: and (3) using a hollowed mask in the spraying process, and doping quantum dots in the liquid of the partial encrypted pattern to obtain the required encrypted information coating.
8. The preparation method of the anti-counterfeit label based on the multilayer quasi-amorphous photonic heterostructure, according to claim 1, is characterized in that: the solvents for realizing the display of the encrypted information are ethanol, silicon oil and SiO2The information is shown by penetrating the solvent into the gap of the multilayer quasi-amorphous photon heterostructure and utilizing ethanol and SiO2The close refractive index property reduces light scattering and makes SiO2The layer is transparent and Fe3O4@SiO2Has high refractive index, has large refractive index contrast with alcohol, and thus exhibits bright structural color, and SiO is volatilized2The layer is gradually restored to the original opaque state, the encrypted information is hidden again, the other switch for showing the encrypted information is UV, and the information encrypted by using quantum dots is only in SiO2The layer is transparent and can be clearly shown in the UV light environment, and the information is invisible in the ambient light.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111251657.1A CN113990844A (en) | 2021-10-25 | 2021-10-25 | Preparation method of anti-counterfeit label based on multilayer quasi-amorphous photon heterostructure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111251657.1A CN113990844A (en) | 2021-10-25 | 2021-10-25 | Preparation method of anti-counterfeit label based on multilayer quasi-amorphous photon heterostructure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113990844A true CN113990844A (en) | 2022-01-28 |
Family
ID=79742106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111251657.1A Pending CN113990844A (en) | 2021-10-25 | 2021-10-25 | Preparation method of anti-counterfeit label based on multilayer quasi-amorphous photon heterostructure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113990844A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008102046A1 (en) * | 2007-02-23 | 2008-08-28 | Consejo Superior De Investigaciones Científicas | Multilayer structure formed by nanoparticular lamina with unidimensional photonic crystal properties, method for the production thereof and use thereof |
| CN110766119A (en) * | 2019-09-27 | 2020-02-07 | 河北师范大学 | Physical unclonable structural color anti-counterfeiting label with multiple anti-counterfeiting modes |
| CN112940308A (en) * | 2021-01-14 | 2021-06-11 | 西安交通大学 | Preparation method of PDMS (polydimethylsiloxane) super-hydrophobic flexible film with switchable transparent/opaque states |
| CN113277845A (en) * | 2021-06-25 | 2021-08-20 | 东北大学 | Method for preparing ultrathin dielectric ceramic film based on particle-free dielectric ceramic ink |
| CN113416450A (en) * | 2021-07-05 | 2021-09-21 | 中钞印制技术研究院有限公司 | Anti-counterfeiting ink and preparation method thereof, anti-counterfeiting layer and preparation method thereof |
-
2021
- 2021-10-25 CN CN202111251657.1A patent/CN113990844A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008102046A1 (en) * | 2007-02-23 | 2008-08-28 | Consejo Superior De Investigaciones Científicas | Multilayer structure formed by nanoparticular lamina with unidimensional photonic crystal properties, method for the production thereof and use thereof |
| CN110766119A (en) * | 2019-09-27 | 2020-02-07 | 河北师范大学 | Physical unclonable structural color anti-counterfeiting label with multiple anti-counterfeiting modes |
| CN112940308A (en) * | 2021-01-14 | 2021-06-11 | 西安交通大学 | Preparation method of PDMS (polydimethylsiloxane) super-hydrophobic flexible film with switchable transparent/opaque states |
| CN113277845A (en) * | 2021-06-25 | 2021-08-20 | 东北大学 | Method for preparing ultrathin dielectric ceramic film based on particle-free dielectric ceramic ink |
| CN113416450A (en) * | 2021-07-05 | 2021-09-21 | 中钞印制技术研究院有限公司 | Anti-counterfeiting ink and preparation method thereof, anti-counterfeiting layer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 温小翔等: "Solvent/UV driven information encryption based on a multilayer quasi-amorphous photonic heterostructure", 《JOURNAL OF MATERIALS CHEMISTRY C》, 22 October 2021 (2021-10-22), pages 1 - 13 * |
| 肖磊;吴卫东;卢铁城;唐永建;蒋晓东;罗炫;方瑜;叶鑫;: "SiO_2胶体晶体自组装技术", 强激光与粒子束, no. 06, 15 June 2010 (2010-06-15) * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | Structural color patterns on paper fabricated by inkjet printer and their application in anticounterfeiting | |
| Wu et al. | Bio-inspired photonic crystal patterns | |
| Gallei | Functional Polymer Opals and Porous Materials by Shear‐Induced Assembly of Tailor‐Made Particles | |
| CN1324094C (en) | Opaque flake for covert security applications | |
| US10933654B2 (en) | Process for isotropic structural colour printing and an apparatus for detecting a target substance in the gaseous phase | |
| CN110072951A (en) | Printing ink composition, light conversion layer and colour filter | |
| CN109021481B (en) | Colored inverse opal structure photonic crystal plastic film with bright pearlescent color and luster, and preparation method and application thereof | |
| US10836918B2 (en) | Microparticles and apparatus for smart ink production | |
| TW200830932A (en) | Composition for color converting member and production method of color conversion substrate using the same | |
| GB2520384A (en) | Quantum dot ink formulation for heat transfer printing applications | |
| CN101360795A (en) | Colourant compositions | |
| CN108608690B (en) | One kind is added lustre to laminated film and its application | |
| KR20100040527A (en) | Pigment for a paint composition consisted of photonic crystals and method for preparing thereof | |
| Pi et al. | Dual-layer nanofilms via mussel-inspiration and silication for non-iridescent structural color spectrum in flexible displays | |
| CN114230954A (en) | Preparation method of bionic stealth nanoparticle doped liquid crystal elastomer film | |
| CN113637362B (en) | Photocurable liquid photonic crystal color paste, preparation method and application thereof in construction of structural color generation film | |
| CN113990844A (en) | Preparation method of anti-counterfeit label based on multilayer quasi-amorphous photon heterostructure | |
| Luo et al. | C-Dot-Embedded SiO2 Concentric Microspheres for Bright Fluorescent Photonic Pigments | |
| Wen et al. | Solvent/UV driven information encryption based on a multilayer quasi-amorphous photonic heterostructure | |
| Takeoka et al. | Structural coloration of a colloidal amorphous array is intensified by carbon nanolayers | |
| CN115083256A (en) | Anti-counterfeit label, composite optical structure, preparation method and application thereof | |
| CN113912896B (en) | Composite anti-counterfeiting film preparation method based on photonic band gap matching | |
| CN113504584B (en) | Multi-mode variable structure color three-dimensional ordered structure color film and preparation method and application thereof | |
| Liang et al. | Self-assembled quantum dot microstructure guided by a microemulsion approach for immunoassays | |
| CN114231281A (en) | Preparation method and application of multicolor cross-linking effect emission long-wave carbon dot powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |