CN114907723A - Fluorescent encryption anti-counterfeiting ink based on halide perovskite quantum dots and preparation method thereof - Google Patents
Fluorescent encryption anti-counterfeiting ink based on halide perovskite quantum dots and preparation method thereof Download PDFInfo
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
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Abstract
The invention relates to a halide perovskite quantum dot-based fluorescence encryption anti-counterfeiting ink and a preparation method thereof, the halide perovskite quantum dot-based fluorescence encryption anti-counterfeiting ink comprises an ink solvent and a fluorescence component, wherein the fluorescence component takes halide perovskite quantum dots doped with element ions as a core, TMOS or APTES coated outside the core as an inner core layer, and PMMA or PS coated outside the inner core layer as an outer core layer; wherein, the doped element ions in the core are rare earth ions or transition metal ions. The fluorescent encryption anti-counterfeiting ink based on the halide perovskite quantum dots has the advantages of good fluorescence characteristic, high stability in the environment, stable multicolor luminescence, high encryption level, long service life and the like.
Description
Technical Field
The invention relates to the field of anti-counterfeiting ink, in particular to fluorescent encryption anti-counterfeiting ink based on halide perovskite quantum dots and a preparation method thereof.
Background
The halide perovskite quantum dot can be used for luminescent LEDs, illumination display, anti-counterfeiting, solar cells, sensors and other photoelectric devices due to the excellent characteristics of high quantum yield, wide color gamut, narrow half-height width, high color purity, high absorption coefficient, simplicity and convenience in synthesis, low cost and the like. However, the halide perovskite quantum dots are easily affected by the environment such as humidity, illumination, temperature and the like, so that the quantum dots are unstable. And due to the ion characteristics, the formed multiple colors are easy to generate ion exchange reaction, so that the synthesized multiple colors are unstable and the application effect is poor.
Disclosure of Invention
The invention provides the fluorescent encryption anti-counterfeiting ink based on the halide perovskite quantum dots and the preparation method thereof in order to make up the defects of the prior art, and the obtained fluorescent encryption anti-counterfeiting ink has the advantages of good fluorescence characteristic, high stability in the environment, stable multicolor luminescence, high encryption level, long service life and the like.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the fluorescent encryption anti-counterfeiting ink based on the halide perovskite quantum dots comprises an ink solvent and a fluorescent component, wherein the fluorescent component takes the halide perovskite quantum dots doped with element ions as a core, TMOS or APTES coated outside the core as an inner core layer, and PMMA or PS coated outside the inner core layer as an outer core layer; wherein the element ions doped in the core are rare earth ions or transition metal ions.
Wherein TMOS is tetramethoxysilane, and APTES is 3-aminopropyltriethoxysilane.
Further, the ink solvent is one of dichloromethane, chloroform and water.
Further, the mass of the ink solvent is 80-95% of the total mass of the fluorescent encryption anti-counterfeiting ink according to mass fraction.
Further, the application also provides a preparation method of the fluorescent encryption anti-counterfeiting ink based on the halide perovskite quantum dots, which specifically comprises the following steps:
s1: adding a certain amount of lead halide, cesium halide, oleylamine and halide salt of a doping element into a polar solvent A, and stirring and mixing to obtain an element ion doped halide perovskite quantum dot solution;
s2: adding TMOS or APTES into the polar solvent B, and stirring and mixing to form a polar solution B1; adding PMMA or PS into a polar solvent B, and stirring and mixing to form a polar solution B2;
s3: quickly injecting a certain amount of the original solution obtained in the step S1 into the polar solution B1, stirring and mixing to obtain an element ion doped halide perovskite quantum dot solution with a nuclear inner layer;
s4: centrifuging the solution obtained in the step S3, re-dispersing the centrifuged precipitate into a B2 solution, stirring and mixing to obtain an element ion-doped halide perovskite quantum dot solution with a nuclear inner layer and a nuclear outer layer, wherein the halide perovskite quantum dot solution can be used as fluorescent encryption anti-counterfeiting ink of a fluorescent component;
or centrifuging the solution obtained in the step S3, re-dispersing the centrifuged precipitate into the B2 solution, stirring and mixing to obtain an element ion doped halide perovskite quantum dot solution with a nuclear inner layer and a nuclear outer layer, adding a certain amount of normal hexane into the solution, stirring to obtain a precipitate, grinding the obtained precipitate into powder, and re-dispersing the powder into water to obtain the fluorescent encryption anti-counterfeiting ink with the fluorescent component.
In one example, the fluorescent encryption anti-counterfeiting ink comprises more than one fluorescent component, wherein different fluorescent components are different in doped element ions, and the preparation method comprises the following steps: the method comprises the steps of preparing the fluorescent encryption anti-counterfeiting ink with different fluorescent components according to the steps of claim 3, and mixing the fluorescent encryption anti-counterfeiting ink with different fluorescent components according to a certain proportion.
Further, the polar solvent A is DMF; the polar solvent B is a low-boiling-point polar solvent; the polar solvent B is CH 2 Cl 2 Or CHCl 3 。
Further, the stirring temperature in the step S1 is 60-95 ℃; in steps S2, S3 and S4, normal temperature stirring is adopted.
Further, in step S1, the halogen element involved is Cl.
Further, the centrifugation speed in step S4 was 7000-15000 rpm.
Further, in step S1, according to the amount of the substance, lead halide is 0.37% to 0.61%, cesium halide is 0.37% to 0.61%, halide salt of the doping element is 0.37% to 0.61%, oleylamine is 0.76% to 1.81%, and the balance is the polar solvent a.
The invention adopts the structure, and has the advantages that:
1. the core material of the fluorescent component in the anti-counterfeiting ink is element ion doped luminescent perovskite quantum dots, so that the luminescent color of the material depends on the doped elements, and the material can emit light with various colors.
The nuclear material is coated with the double-layer protective layer, so that the phenomena of multicolor confusion, color drift and instability caused by anion exchange reaction among halogen elements can be avoided. The respective colors completely depend on the transition luminescence of the doped transition metal element ions or rare earth element ions, and the color of the anti-counterfeiting ink after mixing only depends on the volume ratio or the molar ratio of the solution used before mixing.
Specifically, the core outer layer PMMA or PS has good waterproofness and can form a waterproof protective layer, so that the influence of the external environment on the inner material is avoided; the TMOS or APTES in the core inner layer can better coat the manganese ion doped CsPbCl3 perovskite quantum dots on one hand, and can be used as an interface layer and a regulation ligand to be better compatible with PMMA or PS in the core outer layer on the other hand, so that firm double-layer coating is realized, and the fluorescence stability is good; it should be noted that the material of the inner layer of the core is TMOS or APTES which is soluble in organic solvent and sensitive to water, and can be hydrolyzed into silicon oxide when meeting water, and the silicon oxide has good waterproof property and can be stably coated outside the core, so that the inner layer of the core can still form good waterproof protection for the core even if the waterproof capability of the outer layer of the subsequent core is reduced, thereby being beneficial to realizing strong fluorescence stability of the core material and prolonging the fluorescence life.
2. The anti-counterfeiting ink has strong fluorescence signal, is convenient to identify, and can easily identify the signal under ultraviolet light.
3. The anti-counterfeiting ink can adopt water as an ink solvent, is good in environmental protection, and has the advantages of being good in fluorescence characteristic, high in stability in the environment, long in service life and the like.
4. The anti-counterfeiting ink has the advantages of simple preparation method, low cost, high luminous efficiency, strong quantum dot stability, strong multicolor stability and the like.
Drawings
FIG. 1 is a fluorescence spectrum of a security ink of example 1 of the present invention;
FIG. 2 is a fluorescence spectrum of a forgery-preventing ink according to example 3 of the present invention;
FIG. 3 is a fluorescence spectrum of a forgery-preventing ink according to example 4 of the present invention;
FIG. 4 is a state diagram of the anti-forgery imprint left on filter paper by the anti-forgery ink of example 1 of the present invention;
FIG. 5 is a state diagram of an anti-counterfeit mark left on filter paper by the anti-counterfeit ink of example 3 of the present invention;
FIG. 6 is a state diagram of an anti-counterfeit mark left on filter paper by the anti-counterfeit ink of example 4 of the present invention;
FIG. 7 is a state diagram of the anti-counterfeit mark left on the filter paper by the anti-counterfeit ink of example 5 of the present invention.
Detailed Description
In order to clearly explain the technical features of the present invention, the following detailed description of the present invention is provided with reference to the accompanying drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, however, the present application may be practiced in other ways than those described herein, and therefore the scope of the present application is not limited by the specific embodiments disclosed below.
Example 1:
the embodiment provides a fluorescent encryption anti-counterfeiting ink based on halide perovskite quantum dots, which comprises an ink solvent and a fluorescent component, wherein the fluorescent component is CsPbCl doped with manganese ions 3 Perovskite quantum dots are taken as cores, TMOS coated outside the cores is taken as a core inner layer, and P coated outside the core inner layerMMA as the outer layer of the core, with the ink solvent being dichloromethane.
The preparation method of the fluorescent encryption anti-counterfeiting ink comprises the following steps:
s1: respectively adding 0.5mmol of lead chloride, 0.5mmol of cesium chloride, 0.5mmol of manganese chloride and 0.5ml of oleylamine into 10ml of DMF, and stirring at 90 ℃ for 2 hours to obtain a manganese ion doped CsPbCl3 perovskite quantum dot original solution;
s2: adding TMOS into a polar solvent dichloromethane, mixing, and stirring for 1h to form a TMOS polar solution; adding PMMA into a polar solvent dichloromethane, mixing, and stirring for 1h to form a polar solution of PMMA;
s3: 2ml of manganese ion-doped CsPbCl 3 Quickly injecting the perovskite quantum dot original solution into the TMOS polar solution, and stirring for 2h to obtain the TMOS-coated manganese ion doped CsPbCl 3 Perovskite quantum dot solution;
s4: and centrifuging the solution obtained in the step S3 at 7000-15000rpm for 5min, dispersing the centrifuged precipitate into a PMMA polar solution, stirring for 12h, and performing secondary coating to form a TMOS/PMMA double-layer coated manganese ion doped CsPbCl3 perovskite quantum dot solution which can be used as fluorescent encryption anti-counterfeiting ink.
The fluorescence spectrogram obtained by carrying out fluorescence detection on the fluorescence encryption anti-counterfeiting ink is shown in figure 1.
The obtained fluorescent encryption anti-counterfeiting ink is coated on filter paper, the color can not be seen under the ambient light, the part coated with the anti-counterfeiting ink emits orange-yellow fluorescence with stable color under the irradiation of an ultraviolet lamp with 365nm, and the fluorescence brightness is good, as shown in figure 4; after being placed for 2 months, the mixture is irradiated again by an ultraviolet lamp with 365nm, and the place coated with the anti-counterfeiting ink still emits orange-yellow fluorescence with stable color, and the fluorescence brightness is not attenuated basically; after being placed for 6 months, the fluorescent lamp can still emit orange yellow fluorescence with stable color, and the fluorescence brightness begins to slightly decay.
The fluorescent encryption anti-counterfeiting ink has good fluorescence characteristic and fluorescence stability, wherein the core outer layer PMMA has good waterproofness and can form a waterproof protective layer, so that the influence of the internal material by the external environment is avoided; the TMOS in the core inner layer can better coat the CsPbCl3 perovskite quantum dots doped with manganese ions on one hand, and can be used as an interface layer and a regulation ligand to be better compatible with PMMA in the core outer layer on the other hand, so that firm double-layer coating is realized; it should be noted that the core inner layer material TMOS is soluble in organic solvents and is relatively sensitive to water, and can be hydrolyzed into silicon oxide when meeting water, and the silicon oxide has good waterproof property and can be stably coated outside the core, so that even if the waterproof capability of the subsequent core outer layer is reduced, the core inner layer can still form good waterproof protection for the core, and thus, the core material is beneficial to realizing strong fluorescence stability.
Example 2:
the embodiment provides a fluorescent encryption anti-counterfeiting ink based on halide perovskite quantum dots, which comprises an ink solvent and a fluorescent component, wherein the fluorescent component is CsPbCl doped with manganese ions 3 The perovskite quantum dot is used as a core, TMOS coated outside the core is used as a core inner layer, PMMA coated outside the core inner layer is used as a core outer layer, and the ink solvent is water.
The preparation method of the fluorescent encryption anti-counterfeiting ink comprises the following steps:
s1: respectively adding 0.5mmol of lead chloride, 0.5mmol of cesium chloride, 0.5mmol of manganese chloride and 0.5ml of oleylamine into 10ml of DMF, and stirring at 90 ℃ for 2 hours to obtain a manganese ion doped CsPbCl3 perovskite quantum dot original solution;
s2: adding TMOS into a polar solvent dichloromethane, and stirring for 1h to form a polar solution of TMOS; adding PMMA into a polar solvent dichloromethane, and stirring for 1h to form a polar solution of PMMA;
s3: 2ml of manganese ion-doped CsPbCl 3 Quickly injecting the perovskite quantum dot original solution into the TMOS polar solution, and stirring for 2h to obtain the TMOS-coated manganese ion doped CsPbCl 3 Perovskite quantum dot solution;
s4: and centrifuging the solution obtained in the step S3 at 7000-15000rpm for 5min, dispersing the centrifuged precipitate into a PMMA polar solution, stirring for 12h, performing secondary coating to form a TMOS/PMMA double-layer coated manganese ion doped CsPbCl3 perovskite quantum dot solution, adding a certain amount of normal hexane into the TMOS/PMMA double-layer coated manganese ion doped CsPbCl3 perovskite quantum dot solution, stirring to obtain a precipitate, and dispersing the obtained precipitate in water after grinding to obtain the fluorescent encryption anti-counterfeiting ink.
The obtained fluorescent encryption anti-counterfeiting ink is coated on filter paper, the color cannot be seen under the ambient light, the anti-counterfeiting ink is irradiated by an ultraviolet lamp of 365nm, and the place coated with the anti-counterfeiting ink emits orange-yellow fluorescence with stable color, so that the fluorescence brightness is good; after the anti-counterfeiting ink is placed for 1 month, the anti-counterfeiting ink is irradiated again by an ultraviolet lamp with 365nm, and the place coated with the anti-counterfeiting ink still emits orange-yellow fluorescence with stable color, and the fluorescence brightness is not attenuated basically; after being placed for 4 months, the fluorescent lamp still can emit orange yellow fluorescent light with stable color, but the fluorescent brightness begins to slightly decay.
The ink solvent of the fluorescent encryption anti-counterfeiting ink adopts water, has good environmental protection performance and good fluorescence characteristic and fluorescence stability, wherein the outer layer of the core has good waterproofness and can form a waterproof protection outer layer, the inner layer of the core is made of TMOS which is soluble in organic solvents and is sensitive to water, the core can be hydrolyzed into silicon oxide after meeting water, the silicon oxide has good waterproofness and can be stably coated outside the core to form a good waterproof protection inner layer, and the ink solvent has unique double-layer protection and good stability even if the water is adopted as the ink solvent.
Example 3:
the embodiment provides fluorescent encryption anti-counterfeiting ink based on halide perovskite quantum dots, which comprises an ink solvent and a fluorescent component, wherein the fluorescent component is CsPbCl doped with europium ions 3 The perovskite quantum dots are used as cores, TMOS coated outside the cores is used as a core inner layer, PMMA coated outside the core inner layer is used as a core outer layer, and the ink solvent is dichloromethane.
The preparation method of the fluorescent encryption anti-counterfeiting ink comprises the following steps:
s1: respectively adding 0.5mmol of lead chloride, 0.5mmol of cesium chloride, 0.5mmol of europium chloride and 0.5ml of oleylamine into 10ml of DMF, and stirring at 90 ℃ for 2 hours to obtain a europium ion doped CsPbCl3 perovskite quantum dot original solution;
s2: adding TMOS into a polar solvent dichloromethane, and stirring for 1h to form a polar solution of TMOS; adding PMMA into a polar solvent dichloromethane, and stirring for 1h to form a polar solution of PMMA;
s3: 2ml of europium ion-doped CsPbCl 3 Quickly injecting the perovskite quantum dot original solution into the TMOS polar solution, and stirring for 2h to obtain the TMOS-coated europium ion doped CsPbCl 3 Perovskite quantum dot solution;
s4: and centrifuging the solution obtained in the step S3 at 7000-15000rpm for 5min, dispersing the centrifuged precipitate into a PMMA polar solution, stirring for 12h, and performing secondary coating to form a TMOS/PMMA double-layer coated europium ion doped CsPbCl3 perovskite quantum dot solution which can be used as fluorescent encryption anti-counterfeiting ink.
The fluorescence spectrogram obtained by carrying out fluorescence detection on the fluorescence encryption anti-counterfeiting ink is shown in figure 2.
Coating the obtained fluorescent encryption anti-counterfeiting ink on filter paper, wherein no fluorescence appears under ambient light, irradiating the filter paper by using a 365nm ultraviolet lamp, and emitting red fluorescence with stable color at the position coated with the anti-counterfeiting ink, wherein the fluorescence brightness is good, as shown in figure 5; after being placed for 2 months, the mixture is irradiated again by an ultraviolet lamp with 365nm, and the place coated with the anti-counterfeiting ink still emits red fluorescence with stable color, and the fluorescence brightness is not attenuated basically; after being placed for 6 months, the fluorescent material still can emit red fluorescence with stable color, and the fluorescence brightness starts to slightly decay.
The principle of protection of this embodiment is the same as that of embodiment 1.
Example 4:
the embodiment provides fluorescent encryption anti-counterfeiting ink based on halide perovskite quantum dots, which comprises an ink solvent and a fluorescent component, wherein the fluorescent component is CsPbCl doped with terbium ions 3 The perovskite quantum dots are used as cores, TMOS coated outside the cores is used as a core inner layer, PMMA coated outside the core inner layer is used as a core outer layer, and the ink solvent is dichloromethane.
The preparation method of the fluorescent encryption anti-counterfeiting ink comprises the following steps:
s1: respectively adding 0.5mmol of lead chloride, 0.5mmol of cesium chloride, 0.5mmol of terbium chloride and 0.5ml of oleylamine into 10ml of DMF, and stirring at 90 ℃ for 2 hours to obtain a terbium ion-doped CsPbCl3 perovskite quantum dot original solution;
s2: adding TMOS into a polar solvent dichloromethane, and stirring for 1h to form a polar solution of TMOS; adding PMMA into a polar solvent dichloromethane, and stirring for 1h to form a polar solution of PMMA;
s3: 2ml of terbium ion-doped CsPbCl 3 Quickly injecting the perovskite quantum dot original solution into the TMOS polar solution, and stirring for 2h to obtain TMOS-coated terbium ion-doped CsPbCl 3 Perovskite quantum dot solution;
s4: and (3) centrifuging the solution obtained in the step S3 at 7000-15000rpm for 5min, dispersing the centrifuged precipitate into a PMMA polar solution, stirring for 12h, and performing secondary coating to form a TMOS/PMMA double-layer coated terbium ion doped CsPbCl3 perovskite quantum dot solution which can be used as a fluorescent encryption anti-counterfeiting ink.
The fluorescence spectrogram obtained by carrying out fluorescence detection on the fluorescence encryption anti-counterfeiting ink is shown in figure 3.
Coating the obtained fluorescent encryption anti-counterfeiting ink on filter paper, wherein no fluorescence appears under ambient light, irradiating the filter paper by using a 365nm ultraviolet lamp, and emitting cyan fluorescence with stable color at the position coated with the anti-counterfeiting ink, wherein the fluorescence brightness is good, as shown in figure 6; after being placed for 2 months, the mixture is irradiated again by an ultraviolet lamp with 365nm, the place coated with the anti-counterfeiting ink still emits cyan fluorescence with stable color, and the fluorescence brightness is not attenuated basically; after being placed for 6 months, the fluorescent material still can emit color-stable cyan fluorescence, and the fluorescence brightness begins to slightly decay.
The principle of protection of this embodiment is the same as that of embodiment 1.
As is clear from comparison of examples 1, 3 and 4, in the perovskite quantum dot in which the halide is doped with the elemental ion, the color of the emitted light of the material depends on the transition light emission of the doped element.
Example 5:
the fluorescent anti-counterfeiting inks obtained in the embodiments 3 and 4 are mixed according to the volume ratio or the molar ratio of 1:1, 5:1 and 1:5 respectively, and after mixing, yellow anti-counterfeiting liquid, orange anti-counterfeiting liquid and yellow green anti-counterfeiting liquid can be obtained in sequence. It is thus clear that the color of the mixed security fluid depends on the volume ratio or molar ratio of the different fluorescent security inks before mixing.
The fluorescence encryption anti-counterfeiting ink mixed according to the volume ratio of 1:1 is coated on filter paper, no fluorescence appears under ambient light, and yellow fluorescence with stable color is emitted from the place coated with the anti-counterfeiting ink by irradiation of a 365nm ultraviolet lamp, and the fluorescence brightness is good, as shown in figure 7; after the anti-counterfeiting ink is placed for 1 month, the anti-counterfeiting ink is irradiated again by an ultraviolet lamp with 365nm, the place coated with the anti-counterfeiting ink still emits yellow fluorescence with stable color, and the fluorescence brightness is not attenuated basically; after being placed for 4 months, the fluorescent lamp can still emit yellow fluorescent light with stable color, and the fluorescent brightness begins to slightly decay.
The mixed fluorescent encryption anti-counterfeiting ink has better encryption grade and has the advantages of good fluorescence characteristic, high stability in the environment, stable multicolor luminescence, long service life and the like.
Example 6:
the embodiment provides fluorescent encryption anti-counterfeiting ink based on halide perovskite quantum dots, which comprises an ink solvent and a fluorescent component, wherein the fluorescent component is CsPbCl doped with terbium ions 3 The perovskite quantum dots are used as cores, TMOS coated outside the cores is used as a protective layer, and the ink solvent is dichloromethane.
The preparation method of the fluorescent encryption anti-counterfeiting ink comprises the following steps:
s1: respectively adding 0.5mmol of lead chloride, 0.5mmol of cesium chloride, 0.5mmol of terbium chloride and 0.5ml of oleylamine into 10ml of DMF, and stirring at 90 ℃ for 2 hours to obtain a terbium ion-doped CsPbCl3 perovskite quantum dot original solution;
s2: adding TMOS into a polar solvent dichloromethane, and stirring for 1h to form a polar solution of TMOS; 2ml of terbium ion-doped CsPbCl 3 Quickly injecting the perovskite quantum dot original solution into the TMOS polar solution, and stirring for 2h to obtain TMOS-coated terbium ion-doped CsPbCl 3 The perovskite quantum dot solution is used as fluorescent encryption anti-counterfeiting ink for application test:
the obtained fluorescent encryption anti-counterfeiting ink is coated on filter paper, no fluorescence appears under ambient light, the anti-counterfeiting ink is irradiated by an ultraviolet lamp with 365nm, cyan fluorescence is emitted from the place coated with the anti-counterfeiting ink, the color brightness and the stability are good, but after the anti-counterfeiting ink is placed for 1 month, the anti-counterfeiting ink is irradiated again by the ultraviolet lamp with 365nm, the place coated with the anti-counterfeiting ink can emit cyan fluorescence, but the fluorescence brightness is obviously attenuated.
Example 7:
the embodiment provides fluorescent encryption anti-counterfeiting ink based on halide perovskite quantum dots, which comprises an ink solvent and a fluorescent component, wherein the fluorescent component is CsPbCl doped with terbium ions 3 The perovskite quantum dots are taken as cores, PMMA coated outside the cores is taken as a protective layer, and the printing ink solvent is dichloromethane.
The preparation method of the fluorescent encryption anti-counterfeiting ink comprises the following steps:
s1: respectively adding 0.5mmol of lead chloride, 0.5mmol of cesium chloride, 0.5mmol of terbium chloride and 0.5ml of oleylamine into 10ml of DMF, and stirring at 90 ℃ for 2 hours to obtain a terbium ion-doped CsPbCl3 perovskite quantum dot original solution;
s2: adding PMMA into a polar solvent dichloromethane, and stirring for 1h to form a polar solution of PMMA; 2ml of terbium ion-doped CsPbCl 3 Quickly injecting the perovskite quantum dot original solution into the PMMA polar solution, and stirring for 12h to obtain PMMA-coated terbium ion-doped CsPbCl 3 The perovskite quantum dot solution is used as a fluorescent encryption anti-counterfeiting ink for application test:
the obtained fluorescent encryption anti-counterfeiting ink is coated on filter paper, no fluorescence appears under ambient light, the anti-counterfeiting ink is irradiated by an ultraviolet lamp with 365nm, cyan fluorescence is emitted from the place coated with the anti-counterfeiting ink, the color brightness and the stability are good, but after the anti-counterfeiting ink is placed for 1 month, the anti-counterfeiting ink is irradiated again by the ultraviolet lamp with 365nm, the place coated with the anti-counterfeiting ink can emit cyan fluorescence, but the fluorescence brightness is obviously attenuated.
The above-described embodiments should not be construed as limiting the scope of the invention, and any alternative modifications or alterations to the embodiments of the present invention will be apparent to those skilled in the art. The details of the present invention are not described in detail, but are known to those skilled in the art.
Claims (10)
1. The fluorescent encryption anti-counterfeiting ink based on the halide perovskite quantum dots is characterized by comprising an ink solvent and a fluorescent component, wherein the fluorescent component takes the halide perovskite quantum dots doped with element ions as a core, takes TMOS or APTES coated outside the core as an inner core layer, and takes PMMA or PS coated outside the inner core layer as an outer core layer; wherein the element ions doped in the core are rare earth ions or transition metal ions.
2. The fluorescent encryption anti-counterfeiting ink based on the halide perovskite quantum dots according to claim 1, wherein the ink solvent is one of dichloromethane, chloroform and water.
3. The fluorescent encryption security ink based on halide perovskite quantum dots as claimed in claim 1, wherein the mass of the ink solvent is 80-95% of the total mass of the fluorescent encryption security ink in terms of mass fraction.
4. The preparation method of the fluorescent encryption anti-counterfeiting ink based on the halide perovskite quantum dots is characterized by comprising the following steps:
s1: adding a certain amount of lead halide, cesium halide, oleylamine and halide salt of a doping element into a polar solvent A, and stirring and mixing to obtain an element ion doped halide perovskite quantum dot solution;
s2: adding TMOS or APTES into the polar solvent B, and stirring and mixing to form a polar solution B1; adding PMMA or PS into a polar solvent B, and stirring and mixing to form a polar solution B2;
s3: quickly injecting a certain amount of the original solution obtained in the step S1 into the polar solution B1, stirring and mixing to obtain an element ion doped halide perovskite quantum dot solution with a nuclear inner layer;
s4: centrifuging the solution obtained in the step S3, re-dispersing the centrifuged precipitate into a B2 solution, and stirring and mixing to obtain an element ion-doped halide perovskite quantum dot solution with a core inner layer and a core outer layer, wherein the halide perovskite quantum dot solution is the fluorescent encryption anti-counterfeiting ink based on halide perovskite quantum dots in claim 1;
or centrifuging the solution obtained in the step S3, re-dispersing the centrifuged precipitate into a B2 solution, stirring and mixing to obtain an element ion doped halide perovskite quantum dot solution with a nuclear inner layer and a nuclear outer layer, adding a certain amount of n-hexane into the solution, stirring to obtain a precipitate, grinding the obtained precipitate into powder, and re-dispersing the powder into water to obtain the fluorescent encryption anti-counterfeiting ink based on halide perovskite quantum dots as claimed in claim 1.
5. The preparation method of the fluorescent encryption anti-counterfeiting ink based on the halide perovskite quantum dot, according to claim 4, is characterized in that the fluorescent encryption anti-counterfeiting ink comprises more than one fluorescent component, and different fluorescent components are different in doped element ions, and the preparation method comprises the following steps: the method comprises the steps of preparing the fluorescent encryption anti-counterfeiting ink with different fluorescent components according to the steps of claim 3, and mixing the fluorescent encryption anti-counterfeiting ink with different fluorescent components according to a certain proportion.
6. The preparation method of the fluorescent encryption anti-counterfeiting ink based on the halide perovskite quantum dots according to claim 4 or 5, wherein the polar solvent A is DMF; the polar solvent B is a low-boiling-point polar solvent; the polar solvent B is CH 2 Cl 2 Or CHCl 3 。
7. The preparation method of the fluorescent encryption anti-counterfeiting ink based on the halide perovskite quantum dots according to claim 4 or 5, wherein the stirring temperature in the step S1 is 60-95 ℃; in steps S2, S3 and S4, normal temperature stirring is adopted.
8. The method for preparing fluorescent encryption anti-counterfeiting ink based on halide perovskite quantum dots according to claim 4 or 5, wherein in the step S1, the halogen element is Cl.
9. The method for preparing fluorescent encryption anti-counterfeiting ink based on halide perovskite quantum dots according to claim 4 or 5, wherein the centrifugation speed of the step S4 is 7000-15000 rpm.
10. A preparation method of a fluorescent encryption anti-counterfeiting ink based on halide perovskite quantum dots as claimed in claim 4 or 5, wherein in step S1, according to the mass fraction, lead halide is 0.37% -0.61%, cesium halide is 0.37% -0.61%, halide salt of doping element is 0.37% -0.61%, oleylamine is 0.76% -1.81%, and the balance is polar solvent A.
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