CN115261022A - Single-particle dual-mode NIR (near infrared) excitation up-conversion fluorescent anti-counterfeiting material as well as preparation method and application thereof - Google Patents

Single-particle dual-mode NIR (near infrared) excitation up-conversion fluorescent anti-counterfeiting material as well as preparation method and application thereof Download PDF

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CN115261022A
CN115261022A CN202210948164.1A CN202210948164A CN115261022A CN 115261022 A CN115261022 A CN 115261022A CN 202210948164 A CN202210948164 A CN 202210948164A CN 115261022 A CN115261022 A CN 115261022A
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nayf
counterfeiting
mode
nir
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郝树伟
张海洋
尚云飞
陈童
杨春晖
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7772—Halogenides
    • C09K11/7773—Halogenides with alkali or alkaline earth metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14—Security printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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Abstract

The invention discloses a single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material, and a preparation method and application thereof, and relates to an up-conversion fluorescent anti-counterfeiting material, and a preparation method and application thereof. The fluorescent anti-counterfeiting material aims to solve the technical problem that the anti-counterfeiting security level degree of the existing fluorescent anti-counterfeiting material is low. The single-particle dual-mode NIR excitation up-conversion fluorescence anti-counterfeiting material is NaYF existing in the form of single-particle nano-rods 4 :Yb 3+ /Tm 3+ /Nd 3+ @NaYF 4 :Yb 3+ /Er 3+ The middle area of the nano rod is NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ The two end regions are NaYF 4 :Yb 3+ /Er 3+ . The preparation method comprises the following steps: firstly synthesizing nuclear nano-rods, then carrying out acid cleaning dispersion, and then carrying out epitaxial growth to obtain single-particle dual-mode NIR excitationThe up-conversion fluorescent anti-counterfeiting material has different light emitting conditions under the excitation of different lasers, and the middle part and two ends of a single particle respectively emit blue light and green light, so that the up-conversion fluorescent anti-counterfeiting material can be used in the anti-counterfeiting field.

Description

Single-particle dual-mode NIR (near infrared) excitation up-conversion fluorescent anti-counterfeiting material as well as preparation method and application thereof
Technical Field
The invention relates to an up-conversion fluorescent anti-counterfeiting material and a preparation method and application thereof.
Technical Field
The counterfeit and the inferior goods generally exist in daily life, the bank notes, the documents, the valuables and the like are often counterfeited illegally, the counterfeiting means is continuously innovated along with the development of scientific technology, and even the counterfeiting means can be falsified and truthful, thereby forming serious security threats to individuals, society and countries. Therefore, a safe and reliable anti-counterfeiting encryption and identification method is urgently needed, and an anti-counterfeiting technology which realizes advanced encryption and is difficult to imitate is a major problem at present.
Among many anti-counterfeiting technologies, fluorescent anti-counterfeiting is widely used due to its advantages of low cost, strong recognition capability, no toxicity, difficult simulation, etc. The fluorescent materials currently used mainly include: organic fluorescent materials, carbon quantum dots, metal organic frameworks, up-conversion fluorescent materials and the like, wherein the up-conversion fluorescent materials have the advantages of long fluorescence service life, large anti-Stokes displacement, narrow-band emission, high chemical stability, adjustable excitation and emission signals and the like, and become the most ideal high-grade anti-counterfeiting materials at present. The up-conversion nano material with monochromatic light emission is widely applied to various anti-counterfeiting fields, and the anti-counterfeiting capability is high enough to cope with scenes with low safety requirements. However, for scenes with higher requirements on anti-counterfeiting encryption, the single-luminescent up-conversion material is not enough to meet the requirements on anti-counterfeiting security, because the single-luminescent fluorescent material is easily imitated, and the conventional anti-counterfeiting technology is completed by utilizing a large amount of fluorescent particle aggregates, so that the anti-counterfeiting method is very easy to crack.
Disclosure of Invention
The invention provides a single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material, and a preparation method and application thereof, aiming at the technical problems of low anti-counterfeiting technology, low security level degree and easy imitation of the existing fluorescent anti-counterfeiting material. The single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material has different single-particle light emitting conditions under different laser excitation, and the middle part and two ends of the particle respectively emit blue light and green light. The particles can also be mixed with a single-mode NIR excitation material and the like to obtain anti-counterfeiting patterns with strong fluorescence brightness, good stability and multiple protections, and have important application value in the fields of advanced anti-counterfeiting, encryption and the like.
The single-particle dual-mode NIR excitation upconversion fluorescence anti-counterfeiting material is NaYF existing in the form of a single-particle nanorod 4 :Yb 3+ /Tm 3+ /Nd 3+ @NaYF 4 :Yb 3+ /Er 3+ Wherein the middle region of the nanorod is NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ ，NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ In terms of mole ratio of Y 3+ ：Yb 3+ ：Tm 3+ ：Nd 3+ = (69 to 88.5): (10-25): (0.5-3): (1-3); the two end regions of the nano rod are NaYF 4 :Yb 3+ /Er 3+ ，NaYF 4 :Yb 3+ /Er 3+ In terms of mole ratio of 3+ ：Yb 3+ ：Er 3+ ＝(72～89)：(10～25)：(1～3)。
The single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material disclosed by the invention is excited by 808nm laser, and NaYF in the middle area 4 :Yb 3+ /Tm 3+ /Nd 3+ A single-particle blue fluorescent signal can be emitted; naYF at two end regions under excitation of 980nm laser 4 :Yb 3+ /Er 3+ NaYF in the middle region capable of emitting green fluorescence signal 4 :Yb 3+ /Tm 3+ /Nd 3+ A single particle blue fluorescent signal can be emitted.
The preparation method of the single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material comprises the following steps:
1. NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ And (3) synthesis of the nuclear nanorod:
dissolving 0.4-0.6 g NaOH in 1.2-1.6 mL deionized water, adding 5-8 mL ethanol and 4-6 mL oleic acid, stirring, and then adding 0.8-1.5 mL NH with the concentration of 2-3M 4 Solution F, 1.5-3 mL LnCl with concentration of 0.2-0.3M 3 A solution; wherein LnCl 3 In molar terms in solutionY of ratiometric meter 3+ ：Yb 3+ ：Tm 3+ ：Nd 3+ = (69 to 88.5): (10-25): (0.5-3): (1-3); after stirring, transferring the mixture into a 50mL reaction kettle, and reacting at the temperature of 200-230 ℃ for 12-24 h; naturally cooling to room temperature after the reaction is finished, centrifugally separating, removing supernatant, adding 10-15 mL of ethanol for ultrasonic treatment, and repeating the centrifugal treatment and the ultrasonic treatment for 2-3 times to obtain NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ A core nanorod; then washing the NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ Dispersing the nuclear nano rod in 3-5 ml of cyclohexane for later use;
2. NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ Acid washing and dispersing single particles of the nuclear nanorods:
NaYF dispersed in cyclohexane 4 :Yb 3+ /Tm 3+ /Nd 3+ Transferring the nuclear nanorods into a centrifuge tube, adding ethanol, and centrifuging for 5-10 min under the condition that the rotating speed is 10000-13500 rpm; pouring out supernatant, adding 2M HCl and ethanol into a centrifuge tube, performing ultrasonic dispersion for 10-15 min, centrifuging at 10000-13500 rpm for 10-15 min to perform acid washing, and repeating the acid washing process for 3 times to obtain separated NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ Nuclear nanorod particles of isolated NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ Dispersing the nuclear nano rod particles in deionized water to obtain NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ An aqueous dispersion of core nanorod particles;
3. dual-mode NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ @NaYF 4 :Yb 3+ /Er 3+ Synthesizing the epitaxial structure single-particle nanorod:
1.5-2 mL of EDTA-2 Na2Hl with the concentration of 0.2-0.3M 2 O solution, 0.3-0.5 mL LnCl with the concentration of 0.2-0.3M 3 Solution, 1.8-2.5 mL of NH with the concentration of 2-3M 4 Mixing and stirring the solution F and 3-5 mL of NaF solution with the concentration of 0.5-1M; wherein LnCl 3 Mole ratio of Y in solution 3+ ：Yb 3+ ：Er 3+ ＝(72～89)：(10～25)：(1～3)；
Then adding 0.5-1 mL of HCl with the concentration of 2-3M and 0.5-1 mL of HNO with the mass percentage concentration of 15-23 percent 3 And 0.5-1 mL of NaYF with the concentration of 0.06-0.3M 4 :Yb 3+ /Tm 3+ /Nd 3+ Stirring the aqueous dispersion of the core nanorod particles for 1h;
pouring the mixture into a reaction kettle after stirring, and reacting for 18-24 hours at the temperature of 200-230 ℃; and cooling to room temperature, removing supernatant, centrifugally washing the residual powder with ethanol, and drying to obtain the single-particle dual-mode NIR-excited up-conversion fluorescent anti-counterfeiting material.
The application of the single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material is to apply the single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material to the anti-counterfeiting field.
The anti-counterfeiting method by using the single-particle dual-mode NIR excitation upconversion fluorescence anti-counterfeiting material comprises the following steps:
1. punching uniform small holes on the surface of the anti-counterfeiting pattern mould by adopting a laser drilling technology; single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material or single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material and single-mode NIR excitation material NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ Mixing and filling the mixture into small holes of the anti-counterfeiting pattern; wherein the single-mode NIR excited material NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ In terms of mole ratio of 3+ ：Yb 3+ ：Tm 3+ ：Nd 3+ ＝(69～88.5)：(10～25)：(0.5～3)：(1～3)；
2. The single-particle dual-mode NIR excited up-conversion fluorescent anti-counterfeiting material shows blue fluorescence under the excitation of 808nm and shows green fluorescence under the excitation of 980 nm; local amplification observation is carried out by using a laser confocal microscope, the middle area of a single nanorod of the single-particle dual-mode NIR excited upconversion fluorescent anti-counterfeiting material is blue light, and the two ends of the single nanorod are green light; single-mode NIR excited material NaYF 4 :Yb 3 + /Tm 3+ /Nd 3+ Blue fluorescence is displayed under the excitation of 980nm, and the anti-counterfeiting purpose is achieved by utilizing the characteristic.
The single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material is prepared by modifying single particles, and is encrypted not only in the aspect of fluorescence, but also in the form of single particles and a light-emitting state, so that the anti-counterfeiting is improved to a nanometer level. The single particles are excited by using different wavelengths, and the single particles are different in light emitting conditions under the microcosmic state, so that the difficulty of anti-counterfeiting cracking is greatly improved, and the anti-counterfeiting cracking is extremely difficult to discover. The unique single-particle dual-mode nanorod can realize high-grade encryption of anti-counterfeiting patterns, is extremely difficult to break, and enables the single-particle anti-counterfeiting information to be unobservable under macroscopic view observation.
Compared with the prior art, the invention has the following advantages:
the single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material can be excited at 808nm and 980nm, so that dual-mode excitation is realized, visible light with different colors can be emitted, and the purpose of dual-mode anti-counterfeiting is achieved.
The single particle is modified, the anti-counterfeiting property of the single particle is improved by detecting the light-emitting state of the single particle, and compared with most of fluorescent anti-counterfeiting methods which only adjust the light-emitting color, intensity, service life and the like, the method can be used for carrying out single particle anti-counterfeiting detection in a microscopic state, greatly increases the imitation difficulty, and realizes nano-level single particle encryption.
The shape and color of the fluorescent anti-counterfeiting pattern on the macro scale are firstly utilized to carry out simple anti-counterfeiting encryption, and then the microscopic luminescence condition of the single particle nanorod is observed by utilizing a laser confocal microscope, so that the method is a higher-level anti-counterfeiting encryption method.
The invention has simple equipment and low cost of raw materials, can obtain the anti-counterfeiting pattern by filling the product into the mold, has convenient operation process, can be automatically customized for pattern filling and can be used for more complex anti-counterfeiting patterns.
The single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material can be used in the field of anti-counterfeiting.
Drawings
FIG. 1 shows the NaYF obtained in step two in example 1 4 :20％Yb 3+ /0.5％Tm 3+ /2％Nd 3+ Permeation of core nanorod particlesElectron emission microscope photographs;
FIG. 2 is a transmission electron microscope photograph of the single-particle dual-mode NIR-excited up-conversion fluorescent anti-counterfeiting material obtained in example 1;
FIG. 3 shows NaYF before epitaxy in example 1 4 :Yb 3+ /Tm 3+ /Nd 3+ X-ray diffraction patterns of the nuclear nanorod particles and the single-particle dual-mode NIR-excited up-conversion fluorescent anti-counterfeiting material obtained after epitaxy;
fig. 4 is a schematic diagram of luminescence of a single-particle nanorod of the single-particle dual-mode NIR excitation upconversion fluorescence anti-counterfeiting material prepared in example 1 when observed in a local amplification manner by using a confocal laser microscope;
FIG. 5 shows NaYF before epitaxy in example 1 4 :20％Yb 3+ /0.5％Tm 3+ /2％Nd 3+ And the nuclear nanorod particles and the single-particle dual-mode NIR excited up-conversion fluorescent anti-counterfeiting material obtained after epitaxy form an emission spectrum.
FIG. 6 is a photograph showing the anti-counterfeit pattern of Harbin university of industry school badge prepared in example 1 under the conditions of no laser excitation, 808nm laser excitation and 980nm laser excitation;
FIG. 7 is a partially enlarged luminescent display photograph of the anti-counterfeit pattern of Harbin university of industry school badge prepared in example 1 by a confocal laser microscope; wherein a is filled NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ The powder is obtained under the excitation of 808 nm; b is filled NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ @NaYF 4 :Yb 3+ /Er 3+ The powder is obtained under the excitation of 808 nm; c is filling NaYF 4 :Yb 3+ /Er 3+ The powder is obtained under the excitation of 980 nm; d is filled NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ The powder is obtained under the excitation of 980 nm; e is filled NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ @NaYF 4 :Yb 3+ /Er 3+ The powder gave a pattern under 980nm excitation.
FIG. 8 shows the NaYF obtained by the second step of example 2 4 :20％Yb 3+ /0.5％Tm 3+ /1％Nd 3+ Nuclear nanorod particles and single particles obtained by step threeA transmission electron microscope photo of the sub-dual-mode NIR excited up-conversion fluorescent anti-counterfeiting material;
FIG. 9 shows NaYF before epitaxy in example 2 4 :Yb 3+ /Tm 3+ /Nd 3+ X-ray diffraction patterns of the nuclear nanorod particles and the single-particle dual-mode NIR-excited up-conversion fluorescent anti-counterfeiting material obtained after epitaxy;
FIG. 10 shows NaYF before epitaxy in example 2 4 :20％Yb 3+ /0.5％Tm 3+ /1％Nd 3+ Emitting spectrograms of the nuclear nanorod particles and the single-particle dual-mode NIR-excited up-conversion fluorescent anti-counterfeiting material obtained after epitaxy;
FIG. 11 is a photograph of the "8888" security device of example 2 showing luminescence under excitation of different wavelengths.
Detailed Description
The following examples are used to demonstrate the beneficial effects of the present invention.
Example 1: the preparation method of the single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material comprises the following steps:
1. NaYF 4 :20％Yb 3+ /0.5％Tm 3+ /2％Nd 3+ And (3) synthesis of the nuclear nanorod:
dissolving 0.5g NaOH in 1.5mL deionized water, adding 5mL ethanol and 5mL oleic acid, stirring, and adding 1.0mL NH with concentration of 2M 4 Solution F, 2mL of 0.2M LnCl 3 Solution of LnCl 3 Ln = Y in solution 3+ 、Yb 3+ 、Tm 3 + 、Nd 3+ Molar doping ratio of Y 3+ :Yb 3+ :Tm 3+ :Nd 3+ 20; at the moment, the solution is milky white, stirring is continued for 45min, and after stirring is finished, the solution is transferred to a 25mL reaction kettle and reacts for 12h at the temperature of 220 ℃; naturally cooling to room temperature after the reaction is finished, centrifugally separating, removing supernatant, adding 10mL of ethanol for ultrasonic dispersion treatment, and repeating the centrifugal washing and ultrasonic dispersion treatment for 2 times to obtain NaYF 4 :20％Yb 3+ /0.5％Tm 3+ /2％Nd 3+ A core nanorod; then washing the NaYF 4 :20％Yb 3+ /0.5％Tm 3+ /2％Nd 3+ Dispersing the nuclear nano rod in 4mL of cyclohexane for later use;
2. NaYF 4 :20％Yb 3+ /0.5％Tm 3+ /2％Nd 3+ Acid washing and dispersing single particles of the nuclear nanorods:
NaYF dispersed in 4mL cyclohexane 4 :20％Yb 3+ /0.5％Tm 3+ /2％Nd 3+ The core nanorods were equally divided into 4 samples, and the operation of each sample was as follows: transferring the sample into a 1.5mL centrifuge tube, adding 500 mu L of ethanol, centrifuging for 5min at the rotation speed of 13500rpm, pouring out supernatant, adding 500 mu L of 2M HCl and 750 mu L of ethanol into the centrifuge tube, ultrasonically dispersing for 15min, centrifuging for 15min at the rotation speed of 13500rpm for acid washing, repeating the acid washing process for 3 times to obtain separated NaYF 4 :20％Yb 3+ /0.5％Tm 3+ /2％Nd 3+ Core nanorod particles; 4 parts of separated NaYF 4 :20％Yb 3 + /0.5％Tm 3+ /2％Nd 3+ Dispersing the nuclear nanorod particles in 1mL of deionized water to obtain NaYF 4 :20％Yb 3+ /0.5％Tm 3 + /2％Nd 3+ An aqueous dispersion of core nanorod particles; the microscopic morphology of the single-particle-nucleus nanorod after acid washing is as shown in a transmission electron microscope photo of figure 1, the nanorod is 1.4 mu m long, the end surface diameter is 200nm, and the end surface is flat; in the step of acidizing the nano-rods, a large amount of oleic acid is covered on the surfaces of the untreated nano-rods, so that the nano-rods are agglomerated and adhered together, the subsequent epitaxial growth of single particles is not facilitated, higher-level encryption cannot be performed, and NaYF is subjected to acidizing 4 :20％Yb 3+ /0.5％Tm 3+ /2％Nd 3+ The core nano rod particles are not agglomerated and are uniformly dispersed.
3. Dual-mode NaYF 4 :20％Yb 3+ /0.5％Tm 3+ /2％Nd 3+ @NaYF 4 :20％Yb 3+ /2％Er 3+ Synthesizing the epitaxial structure single-particle nanorod:
1.875mL of EDTA-2 Na2H with a concentration of 0.2M 2 O solution 0.35mL of 2M LnCl 3 Solution, 2.0mL of 2M NH 4 Solution F, 4mL concMixing NaF solution with the degree of 0.5M, stirring and stirring for 45min; wherein LnCl 3 In solution, ln = Y 3+ ,Yb 3+ ,Er 3+ Molar doping ratio of Y 3+ :Yb 3+ :Er 3+ ＝78:20:2；
Then 0.75mL of 2M HCl and 0.75mL of 15% HNO are added 3 And 1mL of NaYF at a concentration of 0.1M 4 :20％Yb 3+ /0.5％Tm 3+ /2％Nd 3+ Stirring the aqueous dispersion of the nuclear nanorod particles for 1h;
after stirring, pouring the mixture into a reaction kettle, and reacting for 18 hours at the temperature of 220 ℃; and cooling to room temperature, removing supernatant, washing white powder at the bottom of the reaction kettle into a 50mL centrifuge tube by using ethanol, centrifuging for 5min at the rotating speed of 8000rpm, pouring out liquid after the centrifugation is finished, adding 10mL ethanol for ultrasonic dispersion treatment, repeating the washing process for 2 times, and finally drying the sample in an oven at 80 ℃ for 8h to obtain the single-particle dual-mode NIR-excited up-conversion fluorescent anti-counterfeiting material.
In this embodiment 1, a transmission electron microscope photograph of the single-particle dual-mode NIR excitation up-conversion fluorescence anti-counterfeiting material obtained after the epitaxial growth in the third step is shown in fig. 2, and it can be seen from fig. 2 that after the single particles dispersed by acid washing are subjected to the epitaxial growth, the end surfaces of the nanorods have been changed from the plane before the epitaxy into an ellipsoid, and the diameter of the end surfaces of the nanorods has not changed, which indicates that the epitaxial growth is performed along the two ends of the nanorods, and after the epitaxial growth, smooth epitaxial ends are grown at the two ends of the nanorods, and the dual-mode single-particle nanorods have been successfully prepared.
Example 1 NaYF before epitaxy 4 :20％Yb 3+ /0.5％Tm 3+ /2％Nd 3+ The X-ray diffraction pattern of the nuclear nanorod particles and the single-particle dual-mode NIR-excited up-conversion fluorescent anti-counterfeiting material obtained after epitaxy is shown in figure 3, and as can be seen from figure 3, the diffraction peaks of the sample after epitaxy are both equal to that of beta-NaYF 4 The standard mapping is well matched, and the method is proved to be capable of controlling and synthesizing the single-particle double-mode nanorod with the hexagonal crystal phase structure.
Single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material in embodiment 1The material NaYF of the epitaxial part 4 :Yb 3 + /Er 3+ No fluorescence is emitted under the excitation of 808nm, green light is emitted under the excitation of 980nm, and NaYF is arranged in the middle part 4 :Yb 3+ /Tm 3+ /Nd 3+ The single-particle dual-mode NIR excited blue light is emitted under the excitation of 808nm and 980nm, and the light-emitting schematic diagram of the single-particle dual-mode NIR excited up-conversion fluorescent anti-counterfeiting material is shown in figure 4. Example 1 NaYF before epitaxy 4 :20％Yb 3+ /0.5％Tm 3+ /2％Nd 3+ The emission spectra of the nuclear nanorod particles and the single-particle dual-mode NIR-excited up-conversion fluorescent anti-counterfeiting material obtained after epitaxy are shown in figure 5, and as can be seen from figure 5, after the epitaxy growth, the overall luminous intensity of the material is obviously improved, and green light peaks appear near 520nm and 540 nm. Under the excitation of 980nm, when the local magnification observation is carried out by a laser confocal microscope, the middle area of the nano rod forming the green pattern is blue light, and the two ends emit green light. The unique single-particle dual-mode nanorod can realize high-grade encryption of anti-counterfeiting patterns, is extremely difficult to break, and enables the single-particle anti-counterfeiting information to be unobservable under macroscopic view observation.
The single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material prepared in the embodiment 1 is used for anti-counterfeiting, and the specific steps are as follows:
1. preparing an anti-counterfeiting pattern by adopting a school badge pattern die of Harbin university, and punching uniform small holes on the surface of the school badge pattern die by adopting a laser drilling technology; the single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material NaYF prepared in the embodiment 1 4 :20％Yb 3+ /0.5％Tm 3+ /2％Nd 3+ @NaYF 4 :20％Yb 3+ /2％Er 3+ And single-mode NIR excited material NaYF 4 :20％Yb 3+ /0.5％Tm 3+ /2％Nd 3+ Mixing according to the mass ratio of 1:1, and coating the mixture into small holes in the middle part of the school badge pattern; excitation of NaYF with single-mode NIR 4 :20％Yb 3+ /2％Er 3+ And (5) coating and filling the mixture into the small holes of the peripheral pattern to obtain the school badge with the anti-counterfeiting pattern.
2. The display photo of the anti-counterfeiting pattern of the school badge of the Harbin university is obtained under the conditions of no excitation, 808nm excitation and 980nm excitation and is shown in figure 6, as can be seen from figure 6, the anti-counterfeiting pattern of the school badge of the Harbin university does not emit light under the condition of no laser excitation, only the middle part of the anti-counterfeiting pattern shows blue fluorescence under the condition of 808nm excitation, and the middle part of the anti-counterfeiting pattern shows green fluorescence under the condition of 980nm excitation, and the periphery of the anti-counterfeiting pattern is different from the middle color, so that the integral observation at a macroscopic angle is the same as that of common fluorescence anti-counterfeiting.
The anti-counterfeit pattern shown in fig. 6 was observed by local magnification using a confocal laser microscope, and the result is shown in fig. 7. A of FIG. 7 shows NaYF under 808nm excitation 4 :Yb 3+ /Tm 3+ /Nd 3+ Single particle luminescence photo, it can be seen that NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ The nanorods only emit blue light, and b in FIG. 7 shows NaYF under 808nm excitation 4 :Yb 3+ /Tm 3+ /Nd 3+ @NaYF 4 :Yb 3+ /Er 3+ In the single particle luminescence photo, it can be seen that the nanorods after epitaxy only emit blue light, which is consistent with the luminescence before epitaxy, and c, d, and e in FIG. 7 show NaYF under 980nm excitation 4 :Yb 3+ /Er 3+ Monochromatic luminescent nano rod, naYF 4 :Yb 3+ /Tm 3+ /Nd 3+ Monochromatic luminescent nanorods and NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ @NaYF 4 :Yb 3+ /Er 3+ A single particle luminescence photo of bicolor luminescent nanorod, wherein NaYF 4 :Yb 3+ /Er 3+ The nano rod only emits green light and NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ The nano rod only emits blue light and NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ @NaYF 4 :Yb 3+ /Er 3+ The nanorods emit blue light in the middle and green light at both ends. The materials involved in the security pattern of the badge and their luminescence are listed in table 1 below.
TABLE 1 materials involved in the anti-counterfeiting pattern of the school badge and the luminescence thereof
Figure BDA0003788180430000071
The single particles are excited by different wavelengths, and the difficulty of anti-counterfeiting cracking is greatly improved by depending on different light emitting conditions of the single particles in a microscopic state, and the single particles are extremely difficult to find. And a dual-mode NIR material can be filled in a small hole, so that only a small part of the whole pattern can be observed to emit unique light of dual-mode NIR single particles under microscopic observation, and the imitation difficulty is greatly improved. The dual-mode single particle material is different from a single mode in light emission, the middle of a single particle of the dual-mode material emits blue light, the two ends of the single particle emit green light, and the dual-mode single particle material has specificity under microscopic observation, and the single-mode material only emits one light, so that the anti-counterfeiting property and the encryption property of the single particle material can be improved by one dimension by utilizing the point. The single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material disclosed by the embodiment 1 can realize multi-level anti-counterfeiting and protect information safety.
Example 2: the preparation method of the single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material comprises the following steps:
1. NaYF 4 :20％Yb 3+ /0.5％Tm 3+ /1％Nd 3+ And (3) synthesis of the nuclear nanorod:
weighing 0.5g of NaOH in a beaker, adding 1.5mL of deionized water, placing on a magnetic stirrer, stirring to dissolve part of NaOH, adding 5mL of ethanol solution, stirring until all NaOH is dissolved, adding 5mL of Oleic Acid (OA), and stirring for 45min;
then 1mL of 2M NH was added 4 F. 2mL of LnCl at a concentration of 0.2M 3 Stirring the solution for 45min, wherein the solution is milky white; wherein LnCl 3 In solution, ln = Y 3+ ,Yb 3+ ,Tm 3+ ,Nd 3+ Molar doping ratio of Y 3+ :Yb 3+ :Tm 3+ :Nd 3+ ＝78.5:20:0.5:1；
Transferring the solution into a 25mL reaction kettle, and reacting for 12h at 220 ℃; taking out the reaction kettle after the reaction is finished, naturally cooling the reaction kettle to room temperature in the air, removing supernatant, washing white powder at the bottom of the reaction kettle into a 50mL centrifugal tube by using ethanol, centrifuging the white powder for 5min at the rotating speed of 8000rpm, pouring out the supernatant after the centrifugation is finished, adding 10mL ethanol to perform ultrasonic dispersion treatment, and repeating the washing and ultrasonic dispersion processes for 2 times to obtain the NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ A core nanorod; then washing the NaYF 4 :20％Yb 3+ /0.5％Tm 3+ /1％Nd 3+ Dispersing the nuclear nanorods in 4mL of cyclohexane for later use;
2. NaYF 4 :20％Yb 3+ /0.5％Tm 3+ /1％Nd 3+ Acid washing and dispersing single particles of the nuclear nanorods:
NaYF dispersed in 4mL cyclohexane 4 :20％Yb 3+ /0.5％Tm 3+ /1％Nd 3+ The sample was divided into 4 portions on average, transferred to a 1.5mL centrifuge tube, added 500. Mu.L ethanol, and centrifuged at 13500rpm for 5min; pouring the solution, respectively adding 500 μ L of 2M HCl and 750 μ L ethanol into a centrifuge tube, ultrasonically dispersing for 15min, centrifuging at 13500rpm for 15min, repeating the acid washing process for 3 times, and finally dispersing the sample in 1mL of deionized water for later use to obtain NaYF 4 :20％Yb 3+ /0.5％Tm 3+ /1％Nd 3+ An aqueous dispersion. The morphology of the dispersed particles is shown in a of fig. 8.
3. Dual-mode NaYF 4 :20％Yb 3+ /0.5％Tm 3+ /1％Nd 3+ @NaYF 4 :20％Yb 3+ /2％Er 3+ Synthesizing the epitaxial structure single-particle nanorod:
1.875mL of EDTA-2 Na2Hwith a concentration of 0.2M was taken 2 O in a 50mL beaker, 0.35mL of 0.2M LnCl was added 3 Solution, 2mL of 2M NH 4 Stirring the solution F and 4mL of NaF solution with the concentration of 0.5M for 45min; wherein LnCl 3 In solution, ln = Y 3+ ,Yb 3+ ,Er 3+ (ii) a Molar doping ratio of Y 3+ :Yb 3+ :Er 3+ ＝78:20:2；
Respectively adding 0.75mL of HCl with the concentration of 2M and 0.75mL of HNO with the mass percentage concentration of 15 percent 3 And 1mL of NaYF at a concentration of 0.1M 4 :20％Yb 3+ /0.5％Tm 3+ /1％Nd 3+ Stirring the aqueous dispersion for 1 hour;
then pouring the mixture into a 25mL reaction kettle, and reacting for 18h at 220 ℃; and after the reaction is finished, taking out the reaction kettle, naturally cooling the reaction kettle to room temperature in the air, removing supernatant, washing white powder at the bottom of the reaction kettle into a 50mL centrifugal tube by using ethanol, centrifuging the white powder for 5min at the rotating speed of 8000rpm, pouring out liquid after the centrifugation is finished, adding 10mL ethanol for ultrasonic dispersion treatment, repeating the washing process for 2 times, and finally drying the sample in an oven at the temperature of 80 ℃ for 8h to obtain the single-particle dual-mode NIR-excited up-conversion fluorescent anti-counterfeiting material.
The scanning electron micrograph of the single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material obtained in this example 2 is shown in b of fig. 8, and comparing a and b of fig. 8, it can be seen that smooth epitaxial portions grow on both ends of the flat end surface after epitaxy.
Example 2 NaYF before epitaxy 4 :Yb 3+ /Tm 3+ /Nd 3+ The X-ray diffraction patterns of the nuclear nanorod particles and the single-particle dual-mode NIR-excited up-conversion fluorescent anti-counterfeiting material obtained after epitaxy are shown in figure 9, and it can be seen that the diffraction peaks of the sample after epitaxy are both equal to that of beta-NaYF 4 The standard map is very good in coincidence, and the method is proved to be capable of controlling and synthesizing the single-particle double-mode nanorod with the hexagonal crystal phase structure.
Example 2 NaYF before epitaxy 4 :Yb 3+ /Tm 3+ /Nd 3+ The emission spectra of the nuclear nanorod particles and the single-particle dual-mode NIR-excited up-conversion fluorescent anti-counterfeiting material obtained after epitaxy are shown in figure 10, and as can be seen from figure 10, the overall luminous intensity of the material is still obviously improved after epitaxy growth, and a strong green peak still appears.
The single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material obtained in the embodiment 2 is used for anti-counterfeiting, and the specific steps are as follows:
1. preparing an anti-counterfeiting pattern by adopting a mold with an '8888' pattern, and punching uniform small holes on the surface of the '8888' pattern mold by adopting a laser drilling technology; the middle two parts with the number of '8' and the whole fourth part with the number of '8' are subjected to the dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material (NaYF) obtained in example 2 4 :Yb 3+ /Tm 3+ /Nd 3+ @NaYF 4 :Yb 3+ /Er 3+ ) With single-mode NIR excited up-conversion fluorescent anti-counterfeiting material (NaYF) 4 :Yb 3+ /Tm 3+ /Nd 3+ ) According to the mass ratio of 1:1, mixing, and smearing to fill small holes; naYF is used for other parts of the mould 4 :Yb 3+ /Er 3+ And (6) filling. Excitation with different wavelengths, the results are shown in fig. 11;
2. "8888" pattern, which does not emit light in the absence of laser excitation;
"8888" pattern of NaYF under 808nm laser excitation 4 :Yb 3+ /Tm 3+ /Nd 3+ @NaYF 4 :Yb 3+ /Er 3+ And NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ The material emits blue light and the pattern shows portions of the middle two "8" and the full appearance of the fourth "8".
"8888" Pattern under 980nm laser excitation, naYF 4 :Yb 3+ /Tm 3+ /Nd 3+ @NaYF 4 :Yb 3+ /Er 3+ And NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ The material emitting blue light, naYF 4 :Yb 3+ /Er 3+ The material emits green light, the pattern appears complete, and the middle two "8" portions and the fourth "8" entirety emit blue light, the remainder emitting green light.
The invention provides a brand-new single-particle dual-mode up-conversion multicolor fluorescence anti-counterfeiting encryption technology for the first time, epitaxial layers with different light-emitting colors are radially and epitaxially grown in one-dimensional nanorod, so that a plurality of areas of a single nanorod can present different signal colors, the method for identifying anti-counterfeiting patterns by irradiation of a conventional light source cannot be implemented, and the anti-counterfeiting security level is improved to a nanoscale by the technology. Only by identifying single particles and patterns formed by the single particles, the anti-counterfeiting whisper can be identified. Therefore, the encryption technology is extremely difficult to crack, the further upgrade of the anti-counterfeiting technology is promoted, and the safety and the reliability of the up-conversion luminescent material in the advanced anti-counterfeiting field can be improved.

Claims (4)

1. A single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material is characterized in that the fluorescent anti-counterfeiting material is NaYF existing in a single-particle nano rod form 4 :Yb 3+ /Tm 3+ /Nd 3+ @NaYF 4 :Yb 3+ /Er 3+ Wherein the middle region of the nanorod is NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ ，NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ In terms of mole ratio of Y 3+ ：Yb 3+ ：Tm 3+ ：Nd 3+ = (69 to 88.5): (10-25): (0.5 to 3): (1-3); the two end regions of the nano rod are NaYF 4 :Yb 3+ /Er 3+ ，NaYF 4 :Yb 3+ /Er 3+ In terms of mole ratio of Y 3+ ：Yb 3+ ：Er 3+ ＝(72～89)：(10～25)：(1～3)。
2. The preparation method of the single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material as claimed in claim 1, which is characterized by comprising the following steps:
1. NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ And (3) synthesis of the nuclear nanorod:
dissolving 0.4-0.6 g NaOH in 1.2-1.6 mL deionized water, adding 5-8 mL ethanol and 4-6 mL oleic acid, stirring, and then adding 0.8-1.5 mL NH with the concentration of 2-3M 4 Solution F, 1.5-3 mL LnCl with concentration of 0.2-0.3M 3 A solution; wherein LnCl 3 Molar ratio of Y in solution 3+ ：Yb 3+ ：Tm 3+ ：Nd 3+ = (69 to 88.5): (10-25): (0.5 to 3): (1-3); after stirring, transferring the mixture into a 50mL reaction kettle, and reacting at the temperature of 200-230 ℃ for 12-24 h; naturally cooling to room temperature after the reaction is finished, centrifugally separating, removing supernatant, adding 10-15 mL of ethanol for ultrasonic treatment, and repeating the centrifugal treatment and the ultrasonic treatment for 2-3 times to obtain NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ A core nanorod; then the washed NaYF is washed 4 :Yb 3+ /Tm 3+ /Nd 3+ Dispersing the nuclear nano rod in 3-5 ml of cyclohexane for later use;
2. NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ Acid washing and dispersing single particles of the nuclear nanorods:
NaYF dispersed in cyclohexane 4 :Yb 3+ /Tm 3+ /Nd 3+ Transferring the nuclear nanorods into a centrifuge tube, adding ethanol, and centrifuging for 5-10 min under the condition that the rotating speed is 10000-13500 rpm; pouring out supernatant, adding 2M HCl and ethanol into a centrifuge tube, ultrasonically dispersing for 10-15 min, centrifuging at 10000-13500 rpm for 10-15 min to perform acid washing, and repeating the acid washing process for 3 times to obtain separated NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ Nuclear nanorod particles of isolated NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ Dispersing the nuclear nano rod particles in deionized water to obtain NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ An aqueous dispersion of core nanorod particles;
3. dual-mode NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ @NaYF 4 :Yb 3+ /Er 3+ Synthesizing the epitaxial structure single-particle nanorod:
1.5-2 mL of EDTA-2 Na2Hl with the concentration of 0.2-0.3M 2 O solution, 0.3-0.5 mL LnCl with concentration of 0.2-0.3M 3 1.8 to 2.5mL of NH with the concentration of 2 to 3M 4 Mixing and stirring the solution F and 3-5 mL of NaF solution with the concentration of 0.5-1M; wherein LnCl 3 Molar ratio of Y in solution 3+ ：Yb 3+ ：Er 3+ ＝(72～89)：(10～25)：(1～3)；
Then adding 0.5-1 mL of 2-3M HCl and 0.5-1 mL of 15-23 mass percent HNO 3 And 0.5-1 mL of NaYF with the concentration of 0.06-0.3M 4 :Yb 3+ /Tm 3+ /Nd 3+ Stirring the aqueous dispersion of the nuclear nanorod particles for 1h;
pouring the mixture into a reaction kettle after stirring, and reacting for 18-24 hours at the temperature of 200-230 ℃; and cooling to room temperature, removing supernatant, centrifugally washing the residual powder with ethanol, and drying to obtain the single-particle dual-mode NIR-excited up-conversion fluorescent anti-counterfeiting material.
3. The application of the single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material as claimed in claim 1, wherein the application is that the single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material is applied to the anti-counterfeiting field.
4. The application of the single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material as claimed in claim 3, wherein the anti-counterfeiting method by using the single-particle dual-mode NIR excitation up-conversion fluorescent anti-counterfeiting material is carried out according to the following steps:
1. drilling uniform small holes on the surface of the anti-counterfeiting pattern die by adopting a laser drilling technology; single-particle dual-mode NIR excitation upconversion fluorescent anti-counterfeiting material, or single-particle dual-mode NIR excitation upconversion fluorescent anti-counterfeiting material and single-mode NIR excitation material NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ Mixing and filling the mixture into the small holes of the anti-counterfeiting pattern; wherein the single-mode NIR excited material NaYF 4 :Yb 3+ /Tm 3 + /Nd 3+ In terms of mole ratio of Y 3+ ：Yb 3+ ：Tm 3+ ：Nd 3+ ＝(69～88.5)：(10～25)：(0.5～3)：(1～3)；
2. The single-particle dual-mode NIR excited up-conversion fluorescent anti-counterfeiting material shows blue fluorescence under the excitation of 808nm and shows green fluorescence under the excitation of 980 nm; local magnification observation is carried out by using a laser confocal microscope, the middle area of a single nanorod of the single-particle dual-mode NIR excited upconversion fluorescence anti-counterfeiting material is blue light, and the two ends of the single nanorod are green light; while single-mode NIR excited material NaYF 4 :Yb 3+ /Tm 3+ /Nd 3+ Blue fluorescence is displayed under the excitation of 980nm, and the anti-counterfeiting purpose is achieved by utilizing the characteristic.
CN202210948164.1A 2022-08-09 2022-08-09 Single-particle dual-mode NIR (near infrared) excitation up-conversion fluorescent anti-counterfeiting material as well as preparation method and application thereof Withdrawn CN115261022A (en)

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